09 Transition Elements Notes 2021

1
12 An introduction to the chemistry of transition elements
This topic illustrates the physical and chemical properties of the transition
elements.
12.1 General physical properties of the first set of transition elements, titanium to
copper
General characteristic chemical properties of the first set of transition elements,
12.2
titanium to copper
12.3 Colour of complexes
12.4 Stereoisomerism in transition element complexes
12.5 Stability constants, Kstab
Transition Elements 
Transition Elements
2
12 An introduction to the chemistry of transition elements

The physical and chemical properties of the transition elements are introduced in this topic.
Learning outcomes
Candidates should be able to:
12.1 General physical a) explain what is meant by a transition element, in terms of d-block
properties of elements forming one or more stable ions with incomplete d
the first set orbitals
of transition
b) sketch the shape of a d orbital
elements, titanium
to copper c) state the electronic configuration of each of the first row transition
elements and of their ions
d) contrast, qualitatively, the melting points and densities of the
transition elements with those of calcium as a typical s-block
element
e) describe the tendency of transition elements to have variable
oxidation states
f) predict from a given electronic configuration, the likely oxidation
states of a transition element
12.2 General a) describe and explain the reactions of transition elements with
characteristic ligands to form complexes, including the complexes of copper(II)
chemical properties and cobalt(II) ions with water and ammonia molecules and
of the first set hydroxide and chloride ions
of transition
b) (i) define the term ligand as a species that contains a lone pair of
elements, titanium
electrons that forms a dative bond to a central metal atom/ion
to copper
including monodentate, bidentate and polydentate ligands
(ii) define the term complex as a molecule or ion formed by a
central metal atom/ion surrounded by one or more ligands
(iii) describe transition metal complexes as linear, octahedral,
tetrahedral or square planar
(iv) state what is meant by co-ordination number and predict the
formula and charge of a complex ion, given the metal ion, its
charge, the ligand and its co-ordination number
c) explain qualitatively that ligand exchange may occur, including the
complexes of copper(II) ions with water and ammonia molecules
and hydroxide and chloride ions
d) describe and explain the use of Fe3+/Fe2+, MnO4–/Mn2+ and
Cr2O72–/Cr3+ as examples of redox systems (see also Section 6.3)
e) predict, using E values, the likelihood of redox reactions
32 www.cie.org.uk/alevel Back to contents page

Cambridge International AS and A Level Chemistry 9701 syllabus Syllabus content
12.3 Colour of a) describe the splitting of degenerate d orbitals into two energy
complexes levels in octahedral and tetrahedral complexes
b) explain the origin of colour in transition element complexes
resulting from the absorption of light energy as an electron moves
between two non-degenerate d orbitals
c) describe, in qualitative terms, the effects of different ligands on
absorption, and hence colour, using the complexes of copper(II)
ions with water and ammonia molecules and hydroxide and
chloride ions as examples
d) apply the above ideas of ligands and complexes to other metals,
given information
12.4 Stereoisomerism in a) describe the types of stereoisomerism shown by complexes,

transition element including those associated with bidentate ligands:
complexes (i) cis-trans isomerism, e.g. cis- and trans-platin Pt(NH3)2Cl2
(ii) optical isomerism, e.g. [Ni(NH2CH2CH2NH2)3]2+
b) describe the use of cisplatin as an anticancer drug and its action by
binding to DNA in cancer cells, preventing cell division
12.5 Stability constants, a) describe and explain ligand exchanges in terms of competing
Kstab equilibria (also see Section 7)
b) state that the stability constant, Kstab, of a complex ion is the
equilibrium constant for the formation of the complex ion in a
solvent from its constituent ions or molecules
c) deduce expressions for the stability constant of a ligand
substitution
d) explain ligand exchange in terms of stability constants, Kstab, and
understand that a large Kstab is due to the formation of a stable
complex ion
Back to contents page www.cie.org.uk/alevel 33

4
 
ESSENTIAL IDEAS
■ The transition elements have characteristic properties; these properties are related to
their all having incomplete d sub-levels.
■ 5
d-orbitals have the same energy in an isolated atom, but split into two sub-levels in a
1
complex ion. The electric field of ligands may cause the d-orbitals in complex ions to split
so that the energy of an electron transition between them corresponds to a photon of
visible light.
13.1 First-row d-block elements – the transition elements

have characteristic properties; these properties are related to their all having
23
9.1 d-block elements
incomplete d sub-levels
block) inand
The d-block
d-block■elements
the periodic
group 13 (p-block)
metalsbetween groups 2 (s-block) and 13 (p-
are found
table
of the and include
periodic some
table (Figure of the
13.1). These mosthave
elements widely
The transition meta
The d-block metals are a group of metals that occur in a large block between group 2 (s-block)
used
similar physical
23.1 The general propert

and chemical properties.
elements in everyday life.
■ Figure 13.1 Position Group 1 2 13 14 15 16 17 18
transition metals
of the d-block metals s-block p-block
Period
in the periodic table
1 H He
2 Li Be B C N O F Ne
3 d-block
Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Learning
Ni Cu Zn Ga Geobjectives:
As Se Br Kr
The elements from titanium to coppe
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba
➔ Describe the characteristic
Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra Rf Db Sg Bh Hs Mt Ds Rgproperties of the
Cn Uut Uuq Uup elements
Uuh Uus Uno
lanthanide elements f-block
actinide elements
titanium to copper.
➔ Explain these in terms of Sc Ti V Cr Mn Fe Co N
The first row of the d-block contains ten elements, scandium to zinc, in which the 3d sub-level
electronic structure.
is being filled with electrons. It is these electrons that are responsible for their characteristic
properties.
Specification reference: 3.2.5
Nine of these elements are classified as transition elements, but the last member of the row, zinc,
does not fully share the properties of the other nine and is not classified as a transition element.
The characteristic properties of the transition elements are:

■ high densities, melting and boiling points
■ the ability to exist in a variety of stable oxidation states; that is, they can form a variety
▲ Figure 1 The d-block elements (shaded)
of ions, both simple ions, for example manganese(ii), Mn2+ (in solid compounds) and (outlined)
Across theoxoanions,
d-block, electrons
for example are being
manganate(vii), MnOadded
4
–
to a d-sub-shell. They
■ the ability to form a variety of complex ions, where the transition metal ion becomes Across a period, electrons are being ad
are metalsdatively
and are good conductors
bonded to molecules or ions of heat Synoptic link
and electricity.
■ the formation of coloured ions (Figure 13.2), both simple and complex
case of titanium to copper). The elem
the ability to act as catalysts (Chapter 6) and increase the rates of chemical reactions
Look back at Topic 8.1,boiling
The Periodic metals. They are good conductors of h
They are■■ hard, strong,
the ability and shiny,
to show magnetism and
in their have
elements high
and melting
compounds and
Table, to revise the blocks of the strong, and shiny, and have high melt
points.
■ the ability to form alloys.
Periodic Table. These physical properties, together wi
These physical properties, together with fairly low chemical reactivity, make these metals extremely useful. E
make these metals extremely useful. steel) for vehicle bodies and to reinfor
and titanium for jet engine parts that
829055_13_IB_Chemistry_451-488.indd 451
Hint Electronic configurations in

18/05/15 10:36 am
Figure 2 shows the electron arrangem

Electron shells are often referred row of the d-block.
to as ‘levels’ or ‘energy levels’. In general there are two outer 4s electr
electrons are added to the inner 3d sub
similarity of these elements. The arrang
copper, Cu, do not quite fit the pattern
and half full (3d5) in Cr and there is on
9.3 Electronic configurations in the d-block elements It is believed that a half-full d-shell ma
same way as a full outer main shell ma
The electron arrangements for the 3d 4s
Sc [Ar] 3d1 4s2
elements in the first row of the d- Electronic configurations o
block is shown on the right.
Ti [Ar] 3d2 4s2
V [Ar] 3d3 4s2
elements
In general there are two outer 4s To work out the configuration of the
Cr [Ar] 3d5 4s1*
electrons and as you go across the down the configuration of the eleme
Mn [Ar] 3d5 4s2
period, electrons are added to the its atomic number.
Fe [Ar] 3d6 4s2
inner 3d sub-shell.
Co [Ar] 3d7 4s2
Ni [Ar] 3d8 4s2 Worked example: Electron co
This is because he 3d sub-shell is at 10 1*
Cu [Ar] 3d 4s Vanadium, V, has an atomic numb
a higher energy level than the 4s sub-
Zn [Ar] 3d10 4s2 configuration is:
shell.
▲ Figure 2 Electronic arrangements of 1s22s22p63s2
the elements in the first d-series. [Ar] The vanadium ion V2+ has lost the
represents the electron arrangement of electron configuration:
argon − 1s22s22p63s23p6 1s22s22p63
Bilal Hameed Transition Elements
Bilal Hameed Marginalizer
366
6
2
9.4 4s vs 3d
As the shells of electrons get further and further from the nucleus,
successive shells become closer in energy. Thus, the difference in
energy between the second and third shells is less than that between
the first and second.
By the time the fourth shell is reached, there is an overlap between the
third and fourth shells.
From potassium onwards, the orbitals of highest energy in the third

shell (i.e. the 3d orbitals) have higher energy than that of lowest energy
in the fourth shell (the 4s orbital).
The transition elements

9.5 4s vs 3d
4p (max. : 6 electrons in 3 orbitals)
Orbitals in
the 4th shell 3d (max. : 10 electrons in 5 orbitals)
4s (max. : 2 electrons in 1 orbital)
Orbitals in
the 3rd shell
3s (max. : 2 electrons in 1 orbital)

Fig 25.1 Relative energy levels of the 3s, 3p, 3d, 4s and 4p orbitals before they contain electrons
Notice the unexpected electron configurations of chromium and copper.

The arrangement of electrons in chromium is [Ar]3d54s1 (Figure 25.3) not
4 2 go into the 4s sub-shell because it occupies a lower energy level
electrons
[Ar]3d 4s which we might have predicted. The explanation of this anomaly
than theelectron
is that the structure [Ar]3d54s1 with half-filled 3d and 4s sub-shells is
3d sub-shell.
more stable than [Ar]3d44s2. The extra stability of a half-filled sub-shell results
fromThis 6 means
9.the 4s that
vs 3d
occupation potassium and calcium
of each orbital have the
by one electron electron
which structure
produces [Ar]4s1
an equal
and [Ar]4sof2 respectively
distribution charge around (Table 15.1).
an atom.
The 3d sub-shell is ‘on average’ nearer the nucleus than the 4s sub-
Copper atoms have an electron structure [Ar]3d104s1 (Figure 25.3) rather than
shell,
Table 4s
[Ar]3d 9 but
15.1
2 at a higher
Electron
. In energy
configurations
this case, level.
it appearsfrom So, once
thatpotassium the
10 13s
[Ar]3d to4szincwithand a 3p
in Period 4sub-shells
filledof3d are
thesub-shell
Periodic
and filled
Table. at argon, further
([Ar] represents
a half-filled electrons
the electronic
4s sub-shell is more go in the
configuration 4s
stable than sub-shell
of [Ar]3d 9 because
4s . the way that thea
2
argon.) Note it has
lower energy level than the 3d
electron configurations for chromiumElectronsub-shell.
and copper
atoms do not fit the general pattern.
Element structure
ElementpotassiumSymbol 3d
Electronic 4s
Hence, and calcium have, respectively, onestructure
and two
electrons in the 4s sub-shell. s,p,d,f notation Electrons-in-boxes
Fig 25.2 Coloured pigments used in the notation
make-up of this tribal dancer include Scandium [Ar]
several compounds of transition elements: Potassium K [Ar]4s1 [Ar] ↑
chromium(III) oxide – green, iron oxides – red ↑
and yellow, manganese salts – violet Calcium
Titanium [Ar] Ca [Ar]4s2 [Ar] ↑
↑
Scandium Sc [Ar]3d14s2 [Ar] ↑ ↑
Chromium [Ar] ↑
Titanium Ti [Ar]3d24s2 [Ar] ↑ ↑ ↑
↑
Iron Vanadium [Ar] V [Ar]3d34s2 [Ar] ↑ ↑ ↑ ↑
Chromium Cr [Ar]3d54s1 [Ar] ↑ ↑ ↑ ↑ ↑ ↑
Transition Elements Manganese [Ar]
Copper Mn [Ar]3d54s2 [Ar] ↑ ↑ ↑ ↑ Bilal
↑ Hameed
↑ ↑
Marginalizer Bilal Hameed
Fig 25.3 The ‘electrons-in-boxes’ representation of the electronic configurations of certain transition metals
↑ ↑
Iron Fe [Ar]3d64s2 [Ar] ↑ ↑ ↑ ↑ ↑ ↑
↑ ↑ ↑
Cobalt Co [Ar]3d74s2 [Ar] ↑ ↑ ↑ ↑ ↑ ↑
electrons go into the 4s sub-shell because it occupies a lower energy level
than the 3d sub-shell.
7 1
This means that potassium and calcium3 have the electron structure [Ar]4s
2
and [Ar]4s respectively (Table 15.1).
Table 15.1 Electron configurations from potassium to zinc in Period 4 of the Periodic
Table. ([Ar] represents the electronic configuration of argon.) Note the way that the
9.7 configurations
electron Electronic configurations
for chromium in the
and copper atoms do d-block elements
not fit the general pattern.
Element
Once Symbol
the 4s sub-shell Electronic
is filled at calcium, electrons structure
enter the 3d level.
s,p,d,f notation Electrons-in-boxes

Therefore, scandium has the electron structure [Ar]3d
go into the 4s sub-shell 1because it occupies4sa ,lower
notation
1 2 titanium has
electrons energy level
the electron
Potassium structure
K [Ar]3d24s
than the 3d sub-shell.
2 and so on.
[Ar]4s [Ar] ↑
Calcium Ca [Ar]4s2 ↑
[Ar] ↑
This means that potassium and calcium have the electron structure ↑[Ar]4s1
14s2
and [Ar]4s2 respectively
Scandium Sc (Table[Ar]3d
15.1). [Ar] ↑ ↑
↑
Table 15.1 Electron configurations from potassium to zinc in[Ar]
Period ↑
4 of the Periodic
Vanadium V [Ar]3d 3 4s2 ↑ ↑ ↑ ↑
Table. ([Ar] represents the electronic configuration of argon.) Note the way that the
Chromium Cr [Ar]3d54s1 [Ar] ↑ ↑ ↑ ↑ ↑ ↑
electron configurations for chromium and copper atoms do not fit the general pattern.
↑
Manganese Mn [Ar]3d54s2 [Ar] ↑ ↑ ↑ ↑ ↑ ↑
Element Symbol Electronic structure
↑ ↑
Iron Fe s,p,d,f64s
[Ar]3d notation
2 Electrons-in-boxes
[Ar] ↑ ↑ ↑ ↑ ↑ ↑
notation
↑ ↑ ↑
Cobalt Co [Ar]3d714s2 [Ar] ↑ ↑ ↑ ↑ ↑ ↑
Potassium K [Ar]4s [Ar] ↑ ↑ ↑ ↑↑
Nickel Ni [Ar]3d824s2 [Ar] ↑ ↑ ↑ ↑ ↑ ↑ ↑
Calcium Ca [Ar]4s [Ar] ↑ ↑ ↑ ↑ ↑ ↑
Copper Cu [Ar]3d104s1 [Ar] ↑ ↑ ↑ ↑ ↑ ↑ ↑
Scandium Sc [Ar]3d14s2 [Ar] ↑ ↑ ↑ ↑ ↑ ↑↑
9. 8
Zinc Electronic
Zn configurations
[Ar]3d104s2 in the [Ar] ↑↑ ↑ ↑elements
d-block ↑ ↑ ↑↑
↑
Vanadium V [Ar]3d34s2 [Ar] ↑ ↑ ↑ ↑
Look carefully at Table 15.1. In Period 4, the d-block elements run from
Chromium(1s22s22pCr
scandium 2) to 5zinc
63s23p63d14s[Ar]3d 4s1 (1s22s22p63s[Ar]
23p↑63d
↑ 10↑4s2↑). But,
↑ ↑ notice
↑
that the electronicMn
Manganese configurations
[Ar]3dof
5 4schromium
2 and
[Ar] copper
↑ ↑ ↑ do ↑ not
↑ ↑fit the
general pattern. The explanation of these irregularities ↑lies in the stability ↑
Iron Fe 6 2
associated with half-filled and[Ar]3d
filled 4ssub-shells. So,[Ar]
the↑ electronic ↑
↑ ↑ ↑ ↑ structure
5 1 ↑ ↑ ↑
ofCobalt
chromium, [Ar]3d Co 4s , with [Ar]3d
half-filled
74s2 sub-shells [Ar]
and↑an ↑equal
↑ ↑ distribution
↑ ↑
ofNickel
charge around Nithe nucleus,[Ar]3d
is more
8 4s2 stable than[Ar]
the ↑electronic
↑ ↑ ↑
structure
↑ ↑ ↑ ↑ ↑ ↑
[Ar]3d4 4s2. 10 1 ↑ ↑ ↑ ↑ ↑
Copper Cu [Ar]3d 4s [Ar] ↑ ↑ ↑ ↑ ↑ ↑
Similarly, the electronic structure of copper, [Ar]3d 10 4s
↑1, ↑with
↑ ↑a ↑filled
↑ 3d
Zinc Zn [Ar]3d104s2 [Ar] ↑ ↑ ↑ ↑9 ↑ 2 ↑
sub-shell and a half-filled 4s sub-shell is more stable than [Ar]3d 4s .
Along the series of d-block elements from scandium to zinc, the number
Look carefully at Table 15.1. In Period 4, the d-block elements run from
of protons in2 the nucleus increases by one from one element to the next.
scandium (1s 2s22p63s23p63d14s2) to zinc (1s22s22p63s23p63d104s2). But, notice
However, the added electrons go into an inner d sub-shell, but the outer
that the electronic configurations of chromium and copper do not fit the
electrons are always in the 4s sub-shell. This means that there are clear
general pattern. The explanation of these irregularities lies in the stability
similarities amongst the transition elements. Changes in their chemical
associated across
properties with half-filled
the series andmuch
are filled less
sub-shells.
marked So,
thanthe
theelectronic structure
big changes across
of chromium, [Ar]3d 54s1, with half-filled sub-shells and an equal distribution
9 ofions
a9.series of elements
p-block d-blocksuch elements
as aluminium to argon.
of charge around the nucleus, is more stable than the electronic structure
[Ar]3d 4 4s2.
When transition metals form their ions, electrons are lost from the 4s
sub-shell before
Similarly, those in the
the electronic 3d sub-shell.
structure
of copper, [Ar]3d10 4s1, with a filled 3d

sub-shell and a half-filled 4s sub-shell is more stable than [Ar]3d94s4 2. 2
E.g. Fe ions have the electron structure [Ar]3d rather than [Ar]3d 4s
2+ 6
Along the series of d-block elements from scandium to zinc, 15.1 the number
The atoms and ions of transition elements 419
andprotons
of V3+ ionsinhave the the electron
nucleus structure
increases [Ar]3d
by one 2 not [Ar]4s2.
from one element to the next.

However, the added electrons go into an inner d sub-shell, but the outer
electrons are always in the 4s sub-shell. This means that there are clear
similarities amongst the transition elements. Changes in their chemical
469983_15_Chem_Y1-2_418-449.indd 419 13/04/1
properties across the series are much less marked than the big changes across
a series of p-block elements such as aluminium to argon.

15.1 The atoms and ions of transition elements 419
8
4
9.10 ions of d-block elements

When empty, the 4s level is energetically more stable than the 3d level.
However, once the 3d level is occupied by electrons, these repel the 4s

electrons even further from the nucleus.
The 4s electrons are therefore pushed to a higher energy level, higher

than the 3d level now occupied.
Hence, when transition metal atoms form ions, they lose electrons from
the 4s level before the 3d level.
9.11 ions of d-block elements 13.1 First-row d-block elements 453
■ Figure 13.3 The 3d

and 4s energy levels on
crossing the first row of
the d-block
25.3 What is
When transition metals form their ions, electrons are lost from the 4s sub-shell
before those in the 3d sub-shell. Thus, Fe2+ ions have the electron structure
[Ar]3d6 (Figure 25.5) rather than [Ar]3d44s2 and V3+ ions have the electron
■ Table 13.2 Outer
structure [Ar]3d2 not [Ar]4s 2
Atomic . At first sight, this seems very
Electron odd because, prior
configuration
electron configurations number
to occupation by electrons, the 4s level is energetically more stable
Element 3d than the 4s
of the first-row d-block
3d level. However, once the 3d level is occupied by electrons, these repel the
metals, where [Ar]
Sc 21 [Ar]3d14s2 [Ar]
represents4s theelectrons
electron evenTi further22from [Ar]3d
the 2nucleus.
4s2 The 4s electrons are therefore
[Ar]
pushed
configuration of the to a higher
V
energy
23
level, higher
[Ar]3d34s2
in fact
[Ar]
than the 3d level now occupied.
noble gas Consequently, when transition metal atoms
argon
9.12 electronic
Cr 24 structures
[Ar]3d54s1 of[Ar]Fe, ions,
form Fe2+they andloseFeelectrons
3+ from
the 4s level before the 3d level.
Mn 25 [Ar]3d54s2 [Ar] Fig 25.4 Iron is an impo
of haemoglobin and pa
Atom/ion Fe 26 Electron structure
[Ar]3d64s2 [Ar]
anaemia may have a die
Co 27 [Ar]3d74s2 3d [Ar] 4s iron. A supplement of ‘i
iron(II) sulfate can help t
Ni 28 [Ar]3d8 4s2 [Ar]
Fe Cu
[Ar] 29 [Ar]3d104s1 [Ar]
Zn 30 [Ar]3d104s2 [Ar]
2+
Fe [Ar]
There are, however, two unexpected or anomalous electron configurations that break the
Aufbau principle, namely, those of chromium and copper. A simple explanation to explain the
Fe3+ existence
[Ar] of these electronic arrangements is to suggest that half-filled and filled 3d sub-levels
are both particularly stable electron configurations.
Fig 25.5 The ‘electrons-in-boxes’ representation of the electronic structures of Fe, Fe2+ and Fe3+
For all the d-block metals the 3d and 4s sub-levels, despite being from different shells, are
relatively close in energy. The low energy difference means that the 3d and 4s electrons can both
This means that all the
be regarded first row
as valence transition
electrons metals
and involved in will have similar chemical
bonding.
properties because
Ions of these are dictated
the d-block by the behaviour of the 4s electrons in the
elements
outermost shell.
When a d-block metal ionizes to form a simple positive ion, the first electrons to be lost are the
Transition Elements 4s electrons,
This horizontal followed
similarity by the 3d
contrasts electrons.
sharply In other
with thewords,
marked whenchanges
a d-block across
metal ionizes,
Bilal aHameedpositive
period of theions
Marginalizer s- are
andformed
p-block possess 4s03d
whichelements, n electron configurations.
such as that from sodium to argon. Bilal Hameed
For example, if the iron(ii) ion is formed, only the two 4s electrons are lost, but if the iron(iii)
ion is formed an additional electron is lost from the spin pair of the 3d sub-level. Some examples
of common d-block simple ions are shown in Table 13.3.
9
5
25.6 Variable oxidation s
The relative stabilities of the +3 and +2 states in manganese and iron can be
KEY POINT
9.13 using
interpreted electronic structuresrepresentation
an ‘electrons-in-boxes’ of Mn, Mn2+ of and Mn3+
their electronic
The important oxidation states fo
structures (Figure 25.10).
each transition metal include +2
Atom/ion Electron structure or +3 or both.
3d 4s
The relative stabilities of oxidatio
states in transition metals can be
interpreted in terms of the stabil
Mn [Ar]
of their electronic structures.
Mn2+ [Ar]
Mn3+ [Ar]
Fe [Ar]
Fe2+ [Ar]
Fe3+ [Ar]
9.14
Fig 25.10 Skill structures
The electron checkof manganese, iron
242and their respective 2+ and 3+ ions
4
3 2 Mn(a)2+Complete
and Fe3+the
each haveconﬁ
electron half-filled 3dfor
gurations orbitals. This
Ni and Ni 2+
. makes them more stable
3+ 2+
than Mn and Fe , respectively. Hence, in manganese the +2 state is more
stable than +3, whereas in iron the +3 3dstate is more stable4sthan +2.
Ni [Ar]
QUESTIONS
5 a Write Ni2+ [Ar]
the electron structures of Cu, Cu+ and Cu2+ using the ‘electrons-in-
boxes’ notation. [2]
(b)b The
In which
presenceoxidation stateinwould
of electrons youisexpect
d orbitals copper
responsible fortothe
becolours
more stable,
of transition element
+1 or +2?
compounds.
c From experience you will know that copper compounds usually exist in
(i)theThe
+2 dstate.
orbitals
Whatin anfactors
isolated transition
might metalthe
increase atom or ion are
relative all at the
stability of same
the +2energy level.
What term is used to describe orbitals that are at the same energy level?
state over the +1 state for copper?
.............................................................................................................................................
6 In section 20.7, we found that E values could be used to predict the
likelihood of redox reactions.
(ii) Complete the diagram 3+
to2+show the splitting of the d orbital energy levels in an octahedral
a Whichcomplex of theion.M (aq)/M (aq) systems in Figure 25.9 will oxidise the
system:
–
15 (aq)Skill
9.2Br →check Br2 (aq) + 2e− E 247 = –1.09 V
4
b Deduce E values of M (aq) →4 M3+(aq) + e− for the systems in
2+
6 2 (a) Cobalt is a transition element and forms compounds with oxidation numbers +2 and +3.
Figure 25.9.
2 (a) Cobalt
Then decide which of these systems could be oxidised by:
is a transition element and forms compounds with oxidation numbers +2 and +3.
energy
2–
Cr2O7 the
Complete (aq) + 14H+structures
electronic (aq) + 6e – 3+
for → 2Cr (aq) + 7H2O(l) for which
Complete the electronic structures for
E = +1.33 V.
a cobalt atom, 2 2 6
1s 2s 2p .................................
a cobalt atom, 1s22s22p6.................................
cobalt in the +3 oxidation state. 1s222s222p66.................................
cobalt in the +3 oxidation state. 1s 2s 2p .................................
(iii) On the axes below, sketch the shapes of one d orbital from the lower energy [2]
level and one
[2]
d orbital from the higher energy level.
(b) (i) In an aqueous solution of cobalt(II) sulfate the cobalt forms complex ions.
lower energy
(b) (i) In an aqueous solutionlevel higher
of cobalt(II) sulfate the cobalt forms energy
complex level
ions.
What is meant by the term complex ion?
What is meant by the term complex ion?
z z
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [1]
....................................................................................................................................... [1]
(ii) State two chemical properties of cobalt, other than the formation of complexes, that are
(ii) not
State two by
shown chemical properties
a typical of cobalt, other than the formation of complexes, that are
s-block element.
not shown by a typical s-block element.
x x
Bilal Hameed.............................................................................................................................................
y y Transition Elements
.............................................................................................................................................
....................................................................................................................................... [2]
....................................................................................................................................... [2]
5 [4]
2+
10
6
9.16 Skill check 7
3 (a) Complete the table to show the total number of unpaired electrons in the 3d and 4s orbitals of
each isolated gaseous atom.
number of unpaired electrons

3d 4s
Cr
Mn
Fe
[2]
(b) Solid potassium manganate(VII), KMnO4, decomposes on heating to form

manganese(IV) oxide, potassium manganate(VI) and a colourless gas.
Construct an equation for this reaction.
.............................................................................................................................................. [2]
(c) Explain the origin of colour in transition element complexes.
9. 17 Skill check
....................................................................................................................................................
....................................................................................................................................................
Q. State the electronic configurations of the following atoms or ions:
....................................................................................................................................................
i....................................................................................................................................................
Cr3+
ii..............................................................................................................................................
Co
[3]
iii V3+
iv Ni2+
v Cu+
9.18 What is a transition element?

While all transition elements 9701/43/O/N/18
© UCLES 2018 are also 3d-block elements, not all[Turn
3d- over
block elements are transition metals.
This is because even though they all share the same physical
properties, they do not share the same chemical properties.
The simple definition of transition metals as ‘d-block elements’ is

incorrect because it leads to the inclusion of scandium and zinc as
transition elements.
Transition Elements Bilal Hameed

11
7

The problem with these two elements (Sc and Zn) is they show some
obvious differences to the other metals in the first row of d-block
elements.
• They have only one oxidation state in their compounds (scandium +3,
zinc +2), whereas the others have two or more.
• Their compounds are usually white, unlike the compounds of

transition metals which are generally coloured.
• They show little catalytic activity.

The formal definition of a transition element is that it is a d-block
element that forms at least one stable ion with a part full d-shell of
electrons.
Scandium only forms Sc3+ (3d0) in all its compounds, and zinc only
forms Zn2+ (3d10) in all its compounds. They are therefore d-block
elements but not transition elements.
Sc 1s2 2s2 2p6 3s2 3p6 3d1 4s2 Zn 1s2 2s2 2p6 3s2 3p6 3d10 4s2
Sc3+ 1s2 2s2 2p6 3s2 3p6 Zn2+ 1s2 2s2 2p6 3s2 3p6 3d10

The reason why all transition elements form a coloured solution is
because their electrons transition from a lower energy state to a higher
energy state in the partially filled d-sublevel.
Therefore, electrons of an element with ions having completely empty

or completely filled d-sublevel will not transition and hence will not be
considered transition metal.
On the contrary, e.g., Fe and Cu have all or at least one ionic form that
has a partially filled d-sublevel, respectively.

the 4th shell 3d (max. : 10 electrons in 5 orbitals) 25.3 What is
Orbitals in 4s (max. : 2 electrons in 1 orbital)
the
When 4thtransition
shell metals form their ions, 3dare
electrons (max.
lost: 10
fromelectrons
the 4s in 5 orbitals)
sub-shell
before those in the 3d sub-shell. 12 Thus, Fe2+ ions 4s (max.
have the: 2electron
electrons in 1 orbital)
structure
[Ar]3d6 (Figure 25.5) rather than [Ar]3d844s2 and V3+ ions have the electron
The transition
The transition
elements elements Orbitals in 2 2
structure [Ar]3d not [Ar]4s . At first sight, this seems very odd because, 4p (max.prior: 6 electrons in 3 orbitals)
the 3rd shell 3p (max. : 6 electrons in 3 the
orbitals)
to occupation by electrons, the 4s level is energetically more stable than
Orbitals
3d level. inHowever, once the 3d
the 3rd shelleven furtherOrbitals inlevel is occupied 3s by electrons,
(max. : 24p
these: 6repel
(max.
electrons 4p
in
the : 6inelectrons
electrons
1(max.
orbital) 3 orbitals)
in 3 orbitals)
4s electrons the from
4th the nucleus. The 4s electrons are therefore
shell
pushed
Fig 25.1 9.
Orbitals 22
Relative d-block
ina higher
to energy
energy levels elements
of level,
the 3s,higher
3p, 3d,in 4sfact
and than the 3d
4p orbitals levelthey
before
3d (max. : 10 electrons in 5 orbitals)
nowcontain
occupied.electrons
Orbitals 4s 1(max. : 2 electrons in 1 orbital)
the 3rd shell
Consequently, whenintransition
Orbitals inmetal atoms form3sions, (max.they
: 2 electrons in
lose electrons orbital)
from
Notice Both
the the
ions 4th
of
unexpected shell
Fe the
have 4th
a
electron shell
partially filled d-orbital, therefore
configurations of chromium 3dFe is
(max.a
and copper.: 10inelectrons
: 103delectrons
(max. 5 orbitals)
in 5 orbitals)
the 4s
Fig 25.1 level
Relative before
energy the 3doflevel.
levels the 3s, 3p, 3d, 4s and 4p orbitals
transition element. 5 before they contain electrons
1 (max.
4s : 2 4s
electrons
(max. : 2in
electrons
1 orbital)
in
The arrangement of electrons in chromium is [Ar]3d 3s (max. :4s (Figurein
2 electrons 3p25.3)
1(max. not
orbital) in 13Iron
Fig 25.4
: 6 electrons orbital)
is an impo
orbitals)
4 2 of haemoglobin and pa
Notice
[Ar]3d the
4s unexpected
which
Atom/ion
Fig 25.1 Relative
we might electron have
energy levels of the 3s, Electron
configurations
predicted.
3p,53d,14s structureThe ofexplanation
and 4p orbitals
chromium before
and
of this copper.
they contain
anomaly
electrons anaemia may have a die
The arrangement
the electronofstructureelectrons[Ar]3d in chromium is half-filled
[Ar]3d 4s3p 5 1
3d(Figure 4s
25.3)
is that 4s 3dwith and: 4s
(max. 63p (max.not
sub-shells
electrons isiron. Ainsupplement
: 6inelectrons
3 orbitals) 3 orbitals)of ‘i
4 2 4 2 iron(II) sulfate can help t
Notice
[Ar]3d the
4s unexpected
which
more stable than [Ar]3d we electron
might
Orbitals have
4s . The configurations
predicted. The of chromium
explanation
in extra stability of a half-filled sub-shell results and
of copper.
this anomaly
The
is arrangement
that
from electronofstructure
theoccupation
the of the
electrons
each3rdorbital
shell
[Ar]3d 5 1
in chromium
by4s one with is half-filled
[Ar]3dwhich
electron 5 1
4s 3d(Figure
and 4s25.3)
produces an not
sub-shells equalis
4 Fe2 [Ar] 4 2
[Ar]3d
more 4s which
stable
distribution than
ofOrbitals
charge weinmight
[Ar]3d around4s .have
Orbitals The
an predicted.
extra stability
in atom. Theof explanation
a half-filledofsub-shell this anomaly results
the 3rdstructure
shell
the shell 5by
3rdorbital 1 3s (max. : 2 electrons in 1 orbital)
is that
from the
the
Copper atoms electron
occupation
have of each [Ar]3d 4s onewith half-filled
electron 10 which
1 3d and
produces 4s sub-shells
an equal is
Fe2+ [Ar] an electron
4 Relative
2
structure [Ar]3d 4s (Figure 25.3) rather than
more stable
9 2 than
distribution of charge[Ar]3d
Fig around
25.1 4s . The
an extra
atom.
energy
[Ar]3d 4s . In this case, it appears that [Ar]3d 4s with3sa(max. stability
levels 10 of
of the 3s,1a3p,
half-filled
3d, 4s andsub-shell
filled 4p orbitals before
3d sub-shell results they contain
25.3 electrons
What is
from the occupation of each orbital by one electron 10 which
1 9 2 :
produces 2 3s
electrons
(max.an : 2inelectrons
equal1 orbital) in 1 orbital)
Copper atoms
and a half-filled
Fe3+ have an
4s sub-shell
[Ar] electron
Notice theisunexpected structure
more stableelectron [Ar]3d
than [Ar]3d 4s (Figure
4s .
configurations 25.3) rather than
of chromium and copper.
distribution
[Ar]3d 9 2Figof
4s . In charge
25.1
this Fig around
Relative
case, 25.1energy
it an
Relative
appears atom.
levelsenergy
of thelevels
that 3s, 3p,
[Ar]3d of 3d,
the
10 4s
4s3s,
1and
3p,
with 4p
3d,orbitals
a4sfilled
and before
4p3d orbitals
they5 before
sub-shell containthey electrons
contain electrons
When
Element transition The
metals
Fig 25.5 The ‘electrons-in-boxes’
arrangement
form their of
ions,
Electron
representation
electrons
electrons
of2+ structure
the
in
are
electronic
chromium
lost from the is 4s[Ar]3d
2+sub-shell 4s1 (Figure 25.3) not
3+
10 structures
1 9 2of Fe, Fe and Fe
Copper
and before atoms
a half-filled
those
Noticehave
in4sthe
the an 3d
Notice electron
sub-shell
[Ar]3d 4
sub-shell.
unexpected
the structure
4sisunexpected
2 more
whichThus, stable
we
electron Fe 3d [Ar]3d
might than
ions have
configurations
electron 4s
[Ar]3d
have (Figure
predicted.
the electron
configurations
of . 25.3)
4s chromium The rather
ofexplanation
structurechromium
and copper.thanand of this anomaly
copper.
9 62 4 2 10 3+1 4s
[Ar]3d
[Ar]3d
Element
4s
This means
. In this
(Figure
The that case,
25.5)
is
arrangement
The
all the
it
rather
that appears
the than
arrangement
first of
rowelectron that
[Ar]3d
electrons [Ar]3d
4s
ofstructure
Electron
transition electrons and
instructure
chromium
metals V4s
[Ar]3d with
ionsis 4s
in chromium
will have
a
1 filled
5 have
[Ar]3d 5
the
withis4s 3d
1 sub-shell
electron
half-filled
[Ar]3d
(Figure 5
4s3d1
25.3)andnot
(Figure 4s25.3)
sub-shells
not i
4 2 sub-shell 4 2is 4than 2seems 9 similar
2 because,chemical
andstructure
a half-filled
properties [Ar]3d
[Ar]3d
because4s not
2 [Ar]4s
4smore which
[Ar]3d
these stable
are4swe more
2. Atthan
which
might
dictated stable
first[Ar]3d
sight,
we
by have this
might
the 4s .
predicted.[Ar]3d
The
have
behaviour very
extra 4s
odd
predicted.
of The
the . electrons
stability
explanation
4s The of prior
a half-filled
explanation
of
in thethis anomaly
ofsub-shell
this resul
anomaly
ured pigments used in the 3d 4s
to occupation
is that by
the electrons,
from
is the
electron
that the the 4s levelstructure
occupation
structure
electron isofenergetically
[Ar]3d each 5 orbital
4s 1
[Ar]3d
with more5
by 1stable
one
half-filled
4s with than
electron thewhich
half-filled
3d and 4s 3d produces
sub-shells
and 4s an equal
sub-shells
is i
is tribal dancer include Scandium
outermost
Element [Ar]
shell. Electron structure
3d level. However,distributiononce the 3dof level
4 is2 occupied
charge 4 2byan
around electrons,
atom. these repel the
ounds of transition elements: This more
horizontal stable
more than
similarity stable
[Ar]3d
contraststhan 4s .
[Ar]3dThe
sharply3dwith extra
4s . The
stability
theelectronsextra
marked changesofstability
a half-filled
of4s a
across a half-filled
sub-shell sub-shell
results resul
ured –pigments used in the– red 4s electrons even further from the nucleus. The 4s are therefore
oxide green, iron
is tribal dancer
oxides Scandium
period
Titanium 9. 23
from
of the d-block
the
[Ar]
s- from
occupation
Copper
and p-blockelements
the occupation
atoms of
elements,each
have orbital
an
such of each by
electron
as that orbital
one electron
by
structure
from sodiumone which
electron
[Ar]3d
to argon.
10produces
4swhich
1
(Figure produces
an25.3)
equalratheran equaltha
anganese salts –include
violet pushed to a higher[Ar] energy level, higher in fact than the 3d level now occupied.
ounds of transition elements: distribution
Consequently, whendistribution
[Ar]3dof charge
9
transition
2
4s . In of
around
charge
this
metal an
case,
atoms around
atom.
it appears
form an atom.
ions, that lose
they [Ar]3d 10
electrons
1
4s with from a filled 3d sub-shell
ured –pigments used in the– red While Cu [Ar]does not half-filled
have a partially filled d orbital and does 10 not 1 form 10a 1 94s2.
+
oxide green, iron oxides Scandium andthe a3d 4s sub-shell is more stable than [Ar]3d
is tribal dancer include Copper
the 4s level
Titanium before atoms
Copper have atoms
level.an electron
have an structure
electron structure
[Ar]3d 4s[Ar]3d(Figure 4s 25.3)(Figure rather 25.3) thanrather tha
anganese salts – violet Chromium coloured[Ar]
[Ar]
25.3
solution, Cu 2+ does, and hence Cu is a transition metal.
ounds of transition elements: [Ar]3d94sElement2
[Ar]3d
. In this9 2
4scase,
. In this
it appears
case, itthat appears [Ar]3d that10 1
4s
[Ar]3dwith
Electron structure
10 1
a
4s filled
with 3d a Fig 25.4
sub-shell
filled 3d Iron is an impo
sub-shell
oxide – green, iron oxides – red Atom/ion Electron structure 9 2 9 2 of haemoglobin and pa
anganese salts – violet Titanium and a[Ar]
Chromium
half-filled
[Ar]
and a half-filled
4s sub-shell 4s sub-shell
is more stable is more
What is a transition
4s
than stable
element? 3d than4s[Ar]3d
[Ar]3d . 4s . anaemia may 4s have a die
Iron [Ar] 3d iron. A supplement of ‘i
Element Element Electron structure
Electron structure iron(II) sulfate can help t
Fig 25.2 Coloured pigments Chromium
used in the [Ar] 3d 3d 4s 4s
Iron [Ar]
[Ar] Scandium [Ar]
make-up of this tribal dancer Copper
include Cu Fe [Ar]
3 The transition metals

several compounds of transitionThe simplest answer to this question is to say that transition elements are those in
elements: In this section y
Fig 25.2 Coloured
Fig 25.2pigments
chromium( Coloured
III) oxideused
–pigments
in the
green, Fig used
iron
Iron 25.3
the in the
The ‘electrons-in-boxes’
‘d-block’
oxides – red of the periodic
[Ar] Scandium representation
table. The of the
neatness electronic
of this configurations
definition lies inof
thecertain
fact transition
that metals
Scandium [Ar]
Titanium [Ar] • Describe what m
make-up ofand
make-up
this yellow,
tribalof
dancer
this tribal
include
manganese dancer Copper
salts –include
violet Cu
Fe+2+
it emphasises [Ar]
[Ar] four
the [Ar]
blocks of elements in the periodic table. This division is
several compounds
several compounds
of transitionofelements:
transition elements: element a trans
green,Fig useful
25.3 Thefor the s-block elements
‘electrons-in-boxes’ in Groups
representation I and
of the II which
electronic are so alike
configurations of in theirtransition metals
certain
25.2
) oxide – green,
chromium(IIIchromium( III) oxide
iron– oxides iron
– red oxides –2+ red • Compare orbita
and yellow, and
manganese
yellow, manganese
salts – violetsaltsCopper
– violet Cu
Fe3+
properties, [Ar]
Titanium
but Titanium
much[Ar]
it isChromium
[Ar] [Ar]
less satisfactory
[Ar] for the elements in the p-block which
how energetica
23.1 The general properties of include metals such as aluminium, reactive non-metals within Group VII and
Ions of the transition metals
Fig 25.3 The The
‘electrons-in-boxes’ representation
representationofofthe
theelectronic
electronic configurations 2+
structures of Fe,ofFecertain 3+
transition metals
25.2
Fig 25.5 ‘electrons-in-boxes’ and Fe
the noble gases. Likewise, the simple definition of transition metals as ‘d-block
Chromium Iron
Chromium [Ar] [Ar]
[Ar]
transition metals
elements’ is also unsatisfactory because it leads to the inclusion of scandium
Ions of the transition metals
This means that all the first row transition metals will have similar chemical
25.2
and zinc as transition elements. As you may have realised already, scandium
properties because these are dictated by the behaviour of the 4s electrons in the
and zincIron
show some Ironobvious
[Ar] differences
[Ar] to the other metals in the first row of
outermost shell. Copper [Ar]
ction you will learn to: Ions of the transition metals
d-block elements.
Q UThis
E S horizontal
TION Fig 25.3 The
similarity ‘electrons-in-boxes’
contrasts sharply with representation
the markedofchanges
the electronic configurations
across a of certain transition
e how electrons are lost • They 9. have only
24
Copper d-blockone oxidation
Copper elements
[Ar] state
[Ar] in their
vs compounds
transition (scandium +3,
elements
ng 4sobjectives:
ection you will
orbital learn
before the to:
3d 1 period
The Look
zinc
of the s-
closely
Q U Eelements
S T I+2),
atand
from
O Nwhereas
Tablep-block
the 25.1.
titanium elements, such as that
to copper
others have two or lie
from the
within
more.
sodium to argon.
d-block elements.
25.2 25.3
Fig 25.3 TheFig 25.3 The ‘electrons-in-boxes’
‘electrons-in-boxes’ representation
representation
of the electronic
of theconfigurations
electronic
2+ configurations
of certain transition
of certain
metals
transition
ribe
e how
when themaking
characteristic
electrons are lost
ions a Which electrons does a calcium atom lose in forming
• Their compounds are usually white, unlike the compounds of transition a Ca ion?
ection you will learn
the to: 1 Look closely atare
Table 25.1.
4s orbital before 3d Q UbEmetals
Si TWhichN electrons
I Owhich would
generally you expect an iron atom to lose in forming
coloured.
erties of the elements Ions of the transition metals
25.2
25.2
e howmaking
when electrons are lost
ions •a They
Which 2+
Feelectrons
anshow ion?
little catalytic a calcium atom lose in forming a Ca2+ ion?
does activity.
um to copper.
e 4s orbital before the 3d 1 b Look closely electrons
iii Which at Table 25.1.would
are lostyou What
expect
in practice an theisFe
by iron aatom?
atom transition
to lose in forming element?
in these
when in terms
making ionsof a Which
an
c Why do youFe 2+ Ions of
electrons
ion? Ions
Sc think
theoftransition
does the transition
metalsmetals
3+a calcium atom lose in forming
Ti V FeCr Mn ionsFeare Comore
Ni Cu stable
Zn than Fe ions?
2+ a Ca2+ ion?
onic structure. b iii Which electrons would are lost you

in expect an
practice by iron
the Fe atom
atom? to lose in forming
In this section you will learn to: 2+ Q U E S T I O N
c are
Why an do ion?
Fe answer 3+ 2+ In this section y
lost you think ions are
Fe question
The simplest to this is more
to say stable than Fe
that transition ions?
elements are those in
ion reference: 3.2.5 how electrons
• Describe
the ii Which
‘d-block’ of electrons
the periodic are
table. lost
The in practice
neatness of by
this the Fe
definitionatom?
lies in the fact that
In this section
Infrom
thisyou
section
the will
4s you
learn
orbital will
to:learn
before the Qto:
3dU Ethe 1 Look closely at Table 25.1. • Describe what m
it emphasises S Tfour
IQOUNblocks
E S T3+I of
O Nelements in the periodic table.2+This division is
orbital when c Why do you think Fe ions are more stable than Fe ions?
a Which electrons does a calcium atom lose in forming a Caelement 2+
ion? a trans
• Describe• how
Describe howmaking
electrons are lostions
electrons are lost
useful for the s-block elements in Groups I and II which are so alike in their
from the from
4s orbital
the 4sbefore
orbital
thebefore
3d the 1 Look 1
closely
Look at
b iless closely
Table
Which 25.1.
at Table
electrons 25.1.
would you in expect an iron • Compare
atom to lose in formingorbita
▲ Figure 1 3d
properties, butd-block
The it is much
elements satisfactory
(shaded)
2+
an Feelectrons
ion?
for
and the
the elements
transition the p-block
metals which
2+ how
2+ energetica
orbital when
orbital
making
whenions
making ions
include metals a Which
such asaelectrons
Which
aluminium, does a calcium
reactive does aatom
non-metals calciumloseatom
within inGroup
forming
loseVIIinand
aforming
Ca ion? a Ca ion?
(outlined) b i Whichb ii
i Which
electrons electrons
would you are
would lost
expect in
youanpractice
expect
the noble gases. Likewise, the simple definition of transition metals as ‘d-blockiron by
atom
an the
iron
to Fe
lose atom?
atomin to
forming
lose in forming
2+ 2+
Across a period,
elements’ is also electrons
an Fe
unsatisfactory
c Why aredo
ion?
an Febeingion?
because
you added
it leads
think Feto tothe
3+ a d-sub-shell
ionsinclusion
are more (3d in
of stable
scandium thantheFe ions?
2+
tic link and
case ofzinc as transition
titanium ii toWhichelements.
iielectrons
copper). Which
TheAs you
aremaylost have
electrons
elements inare realised
practice
from already,
losttitanium
inbypractice
the Fe toscandium
by
atom?
the Feare
copper atom?
and zinc show some obvious differences 3+ to the other3+ metals in the first 2+ row of 2+
462
Transition Elements metals. Theycare Why good c you
do Why think
do you
conductors Fe of ions
think
heatFeareandmore
ions are
stable
more
electricity. than Fe Bilal
stable
They than
ions?
are Hameed
Fe ions?
hard,
ck at Topic 8.1, The Periodic d-block elements.
revise strong, and shiny, and have high melting and boiling points.
462 the462 blocks of the • They have only one oxidation state in their compounds (scandium +3,
Table. These physical
zinc properties,
+2), whereas together
the others with
have two fairly low chemical reactivity,
or more.
13
9
9.25 Characteristics of the transition elements

Transition elements as those elements that form one or more stable
ions with incompletely filled d orbitals.
They show variable oxidation numbers in their compounds.
They form coloured ions in solution.
They can act as catalysts both as the elements and as their

compounds.
They form complex ions.
9.26 Physical & Atomic Properties

s block d-block
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn
Electronic configuration [Ar] 4s1 4s2 3d1 4s2 3d2 4s2 3d3 4s2 3d5 4s1 3d5 4s2 3d6 4s2 3d7 4s2 3d8 4s2 3d10 4s1 3d10 4s2
Melting point/°C 1541 1660 1887 1857 1244 1535 1495 1453 1083 420
Atomic Radius/nm 0.24 0.20 0.16 0.15 0.14 0.13 0.14 0.13 0.13 0.13 0.13 0.13
Density/g cm—3 0.86 1.5 3.0 4.5 6.1 7.2 7.4 7.9 8.9 8.9 9.0 7.1
First IE/kJ mol—1 630 660 650 650 720 760 760 740 740 910
Second IE/kJ mol—1 1240 1310 1370 1590 1510 1560 1640 1750 1960 1730
Third IE/kJ mol—1 2390 2650 2870 2990 3250 2960 3230 3390 3560 3800
9.27 Melting points

The melting and boiling points of the 3d-block metals are generally
much higher than those of the s- and p-block metals.
This is because not only the 4s electrons but also the 3d electrons are
involved in the metallic bonding.
The conductivities of the 3d-block metals are similar to those of

calcium; the conductivity of copper is particularly high.

14
10
9.28 Atomic radii of d-block elements
Because of their similarity it is possible to draw up a list of

characteristic properties of transition elements:
Examiner’s tip points and densities.
The last four properties Across Period 3 from sodium to argon, electrons are being added to the
are most important for compounds/complexes.
outer shell, while the nuclear charge is increasing by the addition of
examinations. protons. The added electrons, entering the outer shell, add not
additional shielding from the extra nuclear charge.
Hence, atomic
in many radii decrease sharply from sodium to argon. At the
reactions.
same time, electronegativities and ionisation energies steadily rise.
The increasing number of outer-shell electrons from sodium to argon

Transition elements form positive ions. The electronic configurations of
The 4s electrons are always also results in major differences in structure and chemical properties
some transition metal ions are shown in Table 4.8.
removed before the 3d electrons from one element to the next.
when an ion is formed.

However, this is not the case with d-block elements. Electrons are
being added into the inner 3d sublevel which increases the shielding
effect towards the outer 4s sublevel.
So while the nuclear charge is increasing across the period in the d-

block, so is the shielding effect of electrons.
The two forces almost cancel each other out and the net result is
roughly equal and relatively small decrease in atomic radii.

15
11
The transition elements can be defined as different from the d-block
elements, and the definition we will use here is:
These are often called transition
a transition element is an element that forms at least one stable
metals rather than transition
9.31 Trends in properties
oxidation state (other than 0) with a partially filled d subshell
elements.
According to this definition, scandium and zinc are not counted as

The increasing inner d electrons across the d-block increase the
transition elements, as the only ion formed by Sc is the 3+ ion, with
shieldingelectronic
effect on the
confi outer1s4s
guration 2 2electrons from
2s 2p63s23p6 (no the increasing
d electrons), nuclear
and that formed
charge, by
keeping the effective nuclear charge almost
2 2constant
6 2 6 across
Zn is the 2+ ion, with electronic configuration 1s 2s 2p 3s 3p 3d10
the d-block.
(full d subshell).
Scandium and zinc do not exhibit some of the characteristic properties
This keeps the atomic
of transition metalsradius, ionisation
detailed below energy
(e.g. they do notand
formelectronegativity
coloured
compounds).
almost constant across the d-block.
We have already studied the variation in properties of a set of eight

elements across the periodic table when we looked at the properties
of period 3 elements. The transition elements also form a set of eight
elements across the periodic table, but these are much more similar to
each other than the elements across period 3. For instance, they are all
metals rather than showing a change from metal to non-metal.
The variation in first ionisation energy and atomic radius of the
transition elements and period 3 elements are compared in Figures 4.23
and 4.24. It can be seen that the variation of ionisation energy and atomic
radius across the series of the transition elements is much smaller than
across period 3.
9.32 Ionisation energy of d-block elements

In period 3, the first ionisation energies follow a general upward trend
from sodium across to argon.
This is caused by an increase in the nuclear charge without an increase

in the number of shielding electrons in the inner orbits.
The effective nuclear charge increases considerably, and this causes a

large increase in the first ionisation energies.
The pattern is different across the d-block.

16
12

The outer electron that is removed in the reaction:
M(g) → M+(g) + e−
is a 4s-electron, and it is shielded by the inner 3d-electrons (as well as
by the 1s-, 2s-, 2p-, 3s- and 3p-electrons).
Although the nuclear charge increases across the block from scandium
to zinc, the number of inner shielding 3d-electrons increases as well.
From Sc to Mn a single electron occupies one of the 3d-orbitals. From Fe to

Zn the electrons pair up and fill the 3d-orbitals. The electron configurations
This means that the first
of chromium ionisation
and copper energies
do not fit the generalof the The
pattern. d-block elements are
explanation
fairly similar. of these irregularities lies in the stability associated with half-filled and
filled sub-shells. So, the electron structure of chromium, [Ar]3d 4s , with
5 1
half-filled 3d and 4s sub-shells is more stable than the electron structure

[Ar]3d44s2. Similarly, the electron structure of copper, [Ar]3d104s1, with
a filled 3d sub-shell and a half-filled 4s sub-shell, is more stable than
[Ar]3d94s2.
Along the series of d-block elements from scandium to zinc, the number of
protons in the nucleus increases by one from one element to the next. The
added electrons go into an inner d sub-shell. The outer electrons are always
in the 4s sub-shell, and this means that the changes in chemical properties
across the series are much less marked than the big changes across a series
of p-block elements such as aluminium to argon. This is clearly illustrated
by the variation in first ionisation energies as shown in the figure below:
2400
He
2200 Ne
2000
1800
1st ionisation energy/kJ mol–1
F
1600 Ar
N Kr
1400
H O Cl
1200 Br
P
C As
1000 Be Zn
S
800 Mg Se
B Si Ge
600
Al
400 Li Na The transition Ga
K Rb
elements
200
0
0 5 10 15 20 25 30 35 40
Chapter 6 Transition elements and qualitative analysis
Atomic number
Figure 6.1 First ionisation energies.
The elements Sc to Zn all react by losing electrons and, since their

ionisation energies are similar, you would expect their chemistry to be
similar. In addition, the chemistry of an element is determined, to a large
extent, by its outer shell electrons – because they are the first to get
involved in reactions. All the d-block elements from Sc to Zn have their
outer electrons in the 4s sub-shell, so they are similar in many ways.
When transition metals form their ions, electrons are lost initially from the
9.36 Successive ionisation
4s sub-shell and not energies
the 3d sub-shell. This may seem somewhat illogical
because, prior to holding any electrons, the 4s level is more stable than
the 3d level. But, once the 3d sub-shell is occupied by electrons, being
There is normally
closer toathe
big jumpthese
nucleus, between
3d electronssuccessive ionisation
repel the 4s electrons energies as
to a higher
a lower shellenergy
loses level. The 4s electrons are, in fact, pushed to an energy level higher
an electron.
than those occupying the 3d sub-shell. So, when transition metals form
ions they lose electrons from the 4s orbital before the 3d level. Because
For example,ofthere
this, it isisusual
a big jump
to write the between the
ground state of thesecond and with
transition metals third
the 3d electrons listed before the 4s. For example, iron is normally written
ionisation energies 6 of 2 magnesium2 (electron structure: 1s 2 2s
as [Ar]3d 4s rather than [Ar]4s 3d . This further emphasises the fact that
6 2 2p6 3s2)
transition metals have similar chemical properties, which are dictated by
because thethethird electron
behaviour has
of the 4s to come
electrons in theirfrom the second shell.
outer shells.
116
This electron is subjected to a much stronger pull from the nucleus as it
is much less shielded.

17
13
9.37 Successive ionisation energies

The energy levels of the 3d- and the 4s-electrons are very similar in d-
block elements and so there is no big jump in successive ionisation
energies from 4s- to 3d-.
The big jump comes after all the 4s- and all the 3d-electrons have been
removed.
The numbers in bold in the next slide refer to the first 3p-electron being
removed.
9.38 Successive ionisation energies

−1
INORGANIC CHEMISTRY
Table 5.3 Difference in successive ionisation energies in kJ mol

Figure 24.2 Melting and boiling points of the
3d-block metals 3000
boiling point
temperature/°C
2000
Titanium Vanadium Chromium Manganese

1000 melting point
([Ar] 3d2 4s2) ([Ar] 3d3 4s2) ([Ar] 3d5 4s1) ([Ar] 3d5 4s2)
0
Sc Ti V Cr Mn Fe Co Ni Cu Zn
the end of the block have the highest densities, as they have the smallest atomic radii
and the highest relative atomic masses.
There is no obvious trend in the M2+ ionic radii, but the M3+ ionic radii tend to
decrease across the block as the nuclear charge increases and attracts the electrons
25_02 Cam/Chem AS&A2
1st and 2nd 649 720 937* 794

more strongly. This decrease in ionic radius is accompanied by an increase in charge
density
Barking of
Dogthe ion, leading to an increased stability of the complexes formed towards
Art
the right of the block.
Ionisation energies
A graph of ionisation energies against proton number (see Figure 24.3) shows three
main features.
2nd and 3rd 1410* Figure 24.3 Ionisation energies of the

3d-block metals
1500* 4000 third IE
1400 1740*
ionisation energy/kJ mol–1
3000
3rd and 4th 1450 1730 2000
1000
second IE
first IE
1780 1940
0
4th and 5th 5450 1680 2300 2170

Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn
The first and second ionisation energies increase only slightly across the block.
The second ionisation energies are only slightly higher than the first.
25_03 Cam/Chem AS&A2
The third ionisation energies are significantly higher, and show a characteristic
d-subshell
Barking pattern.
Dog Art
5th and 6th 6120

The first ionisation energies involve the removal of a 4s electron. This is outside the 3d
subshell and is partially screened by it. As the nuclear charge increases across the block,
the additional d electrons shield the effect of the increasing nuclear charge so that the
4s electron experiences only a small extra attraction. The same effect is shown by the
1630 2390
second ionisation energies, with the exception of those for chromium and copper −
these have rather higher second ionisation energies because the second electron being
6th and 7th 7900 1750

removed is a 3d electron, which does experience the increased nuclear charge.
The third ionisation energies involve the removal of a 3d electron. The pattern
of five values steadily rising, followed by a drop and then five more steadily rising,
mirrors the ionisation energies involving the removal of 2p electrons on crossing
400
7th and 8th 181333_24_A_Chem_BP_397-414.indd 400 10/10/14 8:56 PM

7300
The * refers to the first 3d-electron being removed.
8000
Difference in energy/kJ mol–1
3p-electron being removed

7000
6000
5000 Successive ionisation energies of Mn & Mg

9.39
4000
3000
2000
1000
0
2nd – 1st 3rd – 2nd 4th – 3rd 5th – 4th 6th – 5th 7th – 6th
Figure 5.3 The difference in successive ionisation energies for chromium
Common chemical properties of transition

metals
Variable oxidation states
Bilal HameedThe metals in the s-block exist in only one oxidation state in their compounds — for Transition Elements
st possess a lone pair Bilal Hameed
example, sodium is always +1 and magnesium is always +2. Marginalizer
A complex ion consists of a central transition metal ion surrounded by
The non-transition d-block metals also have a single oxidation state. Zinc is always
ligands.
+2 in its compounds and scandium is always +3.
Nature of Science Looking for trends and discrepancies – the anomalous behaviour of zinc, chromium
and copper
The elements from scandium to zinc form the first row of the d-block (3d-block). The first row
18
of this block contains ten elements, because the 3d sub-level contains five 3d orbitals, each
14
able to accommodate two electrons (a spin pair). All of the elements from scandium to copper
are in the d-block because the 3d sub-level is being progressively filled. Originally the d-block
was known as the ‘transition metals’ because some of their properties show a gradual change
between the reactive metal calcium in group 2 to the much less reactive metal gallium in
group 13. The term ‘transition metal’ is now reserved for those metals in the d-block that show
properties characteristically different from those in the s- and p-blocks (the representative
9.40 calcium vs transition elements
elements). Table 13.4 compares the properties of a typical transition element with calcium.
■ Table 13.4
Property Transition element Calcium
Comparison of a
Melting point Very high (>1000 °C) Lower than transition elements (850 °C)
typical transition
element with calcium Density Very high Lower than transition elements
Atomic radius Smaller than calcium Larger than transition elements
Ionic radius (M2+ ion) Smaller than calcium Larger than transition elements
First ionization energy Larger than calcium Smaller than transition elements
Electrical conductivity Good, but poorer than Very good – better than most transition elements
calcium
Zinc is a d-block element that is excluded from being classified as a transition element.
A transition element is defined as a d-block metal that forms at least one stable cation with an
incomplete 3d sub-level. Zinc forms only the colourless Zn2+ ion, isoelectronic with the Ga3+
ion, with ten electrons in the 3d sub-level.
By contrast, copper, [Ar]3d104s1, forms two simple ions (cations). In the copper(i) ion (Cu+)
the electronic configuration is [Ar]3d10. However, the more common copper(ii) ion (Cu2+) has
the structure [Ar]3d9. Copper is classified as a transition metal because the Cu2+ ion has an
9.41 Skill check

Describe and explain how the density and melting point of cobalt
compare to those of calcium.
829055_13_IB_Chemistry_451-488.indd 454 18/05/15 10:36 am
9.42 Variable oxidation states

Transition metals from Ti to Cu have electrons of similar energy in both
the 3d and 4s levels.
This means that one particular element can form ions of roughly the
same stability by losing different numbers of electrons.
Thus, all the transition metals from titanium to copper exhibit two or
more oxidation states in their compounds.
The maximum stable oxidation state frequently corresponds to the

maximum number of electrons (3d and 4s) available for bonding. For
example, manganese (3d54s2) has a maximum oxidation state of +7.

19
15
The stability of the of

The stability +2the
oxidation state relative
+2 oxidation to the to
state relative +3the
and+3higher states states
and higher
increases from left
increases fromto left
right
toacross the series.
right across This reflects
the series. the increasing
This reflects the increasing
Oxidation states of transition metals
Oxidation states of transition metals

9.43 Variable
difficulty of removing
difficulty oxidation
a 3d electron
of removing states
as the as
a 3d electron nuclear chargecharge
the nuclear increases.
increases.
The table
The below showsshows
table below all oxidation states states
all oxidation of the of
first
theseries of d block
first series of d block
The positive oxidation numbers (oxidation states) exhibited by the
elements. The ones
elements. Theshown in bold
ones shown inare most
bold are common oxidation
most common states states
oxidation of of
transition elements are shown below.
the elements.
the elements.
Element
Element Sc Ti
Sc V
Ti Cr
V Mn
Cr Fe
Mn Co
Fe Ni
Co Cu
Ni Zn
Cu Zn
TIP Oxidation statesstates
Oxidation +7 +7
ndiumScandiumto zinctoare zinctheare the +6 +6
+6 +6
formula for the oxide corresponding to the highest expected
ments in
elements
state for:
the first
in the series
first of
series of +5 +5
+5 +5
+5 +5
d block, but scandium
the d block, but scandiumand and +4 +4 +4 +4 +4 +4 +4
+4
are zincd block elements,
are d block not not
elements, In examining the+3d-block
+3elements
+3 thus+3 far, we+3 +3 on+3one +3
have touched +3 +3
sition elements.
transition Transition
elements. Transition characteristic property
+2 of transition
+2 +2 elements—their
+2 +2 ions +2 can exist
+2 in variable
+2 +2 +2 +2
ments form at
elements least
form at one
leastionone ion oxidation states.
half-equation for the conversion of each of the following +1 +1of other characteristic +1 +1
n an incomplete
with
metals to d subshell.
antheincomplete
different d subshell.
oxidation state. In addition to this property, there are a number
properties of transition elements:
ndium
o Fe Scandium
3 and zinc andform
zincions
formwithions with
In general, the compounds
In general, the compounds of the of
higher oxidation
the higher states are
oxidation statesfound in covalent
are found in covalent
tytoempty
or
Mnincomplete
2 d subshells.
or incomplete d subshells.
compounds and and
compounds molecular
2 metals.and ions
molecular and
ions they
and can
theyact as
can oxidising
act as agents
oxidising as the
agents as the
first3 transition
o VThe seriesseries
first transition runs runs
transition metal metal
transition can gain canelectrons and beand
gain electrons reduced to lower
be reduced oxidation
to lower states.states.
oxidation
mthetitanium
from theto
role oftitanium copper.
to copper.catalyst in the catalytic
platinum–rhodium
of a car. 4 Write the formula for the oxide corresponding to the highest expected
Vanadium chemistry
Vanadium chemistry
oxidation state for:
age of the industrial production of sulfuric acid, sulfur dioxide gas
a Ti oxidation states
Vanadium
d to sulfur trioxide gas in the presence of a catalyst ofVanadium has 4 has
Variable major oxidation
4 major states,states,
oxidation +2, +3,+2, +4+3,
and+4+5. andThe +5.molecular
The molecular
m(V) oxide. The catalyst is used in pellets and the gaseous mixture
b Ni
over layers, or beds, of catalyst. The equation and simple
for this and ions
simple
Transition
reaction below
ions below
is: elements show
can vanadium
formshow
ions with in these
vanadium
a variety in oxidation
thesestates
of oxidation states states
oxidation with the
(oxidation with the
c Cr All transition elements can form ions with an oxidation number of
numbers).
O2(g) 2SO3(g) colourcolour
in aqueous
in solution.
aqueous solution.
9.44 Variable oxidation states
s the vanadium(V) oxide used in pellets rather than as a5
2, and,
Write
oxidation
in the
addition,
numbers.
transition metals
each element
half-equation
From
for thecan
titanium
to the
form a number
conversion of eachof
to manganese,
different
ofions with other
the following
the maximum oxidation
oxidation state.
mass?
OxidationOxidation
number Name
possibleof
Nameis equalof to the total number of 4s and 3d Colour
electrons. For in aqueous
Colour in aqueous
TIP 2
a Fethe
example, Fe3
tomaximum oxidation number possible for titanium ([Ar]3d2 4s2)
can Youremember
can rememberthe colours
the colours
Some common oxidation states for the transition elements and
V2O5 a homogeneous or heterogeneous catalyststate in this state
reaction?
is 4band
molecular
for4manganese
MnO to Mn
ion
molecular2 ion 5 2 Formula
([Ar]3d 4s ) it is 7.
of
Formulaion of solution
ion solution
possible advantage could be gained by passing the gas mixture
anadium
everal beds using
of vanadium using
of catalyst? ‘You Better +5
‘You Better compounds in which these oxidation states occur:
+5 c Dioxovanadium(V)
TABLE VO
2
toDioxovanadium(V)
3.2.2 SOME V3 COMMON ion ionVO+ VO+ Yellow Yellow
OXIDATION 2STATES2 FOR THE TRANSITION
Vanadium’.
Get Vanadium’. Y in you is you
Y in yellow,
is yellow, Vanadate(V)
6ELEMENTS
Describe AND
the ion
Vanadate(V)
COMPOUNDS
role ion IN WHICHVO −3 THESE
of the platinum–rhodium VO − OXIDATION STATES OCCUR
catalyst
3 in the catalytic
better is blue,
B in better is Gblue,
in get G inis get is +4 converter
+4 Oxovanadium(IV)
Ti V of a car.
Oxovanadium(IV)
Cr ion Mn ion VO 2+
Fe VO Co2+ Blue
Ni Blue
Cu Demonstration 3.1
SITION METAL COMPLEXES
Oxidation states of vanadium
en green
and V and
in vanadium
V in vanadium is violet.is violet.+3 7 InVanadium(III)
+3 one stage of the ion
Vanadium(III)industrial
ionproduction
V 3+ of V sulfuric
3+ acid, sulfur
Green dioxide
+1gas
Green and manganese
etal ions are characteristically small and highly charged. This is oxidized to sulfur trioxide gas in the presence of a catalyst of Cu2O
o Try
create
ensity your
results in anown
to create your
abilityrhyme
own rhyme
to strongly +2 and +2
attract ions small Vanadium(II)
vanadium(V)Vanadium(II)
oxide.ion ion
The catalyst V 2+ in pellets
is used V 2+ and the Violet
gaseousViolet
mixture
+2 +2 +2 +2 +2 +2 +2 +2
emonic)
forming for
es,(mnemonic) this
a complexforif ion
youincannot
this ifwhich
you coordinate
cannot (dative) is passed over layers, or beds, of catalyst. The equation for this reaction is:
TiCl2 VCl2 CrCl2 MnCl2 FeSO4 CoCl2 NiSO4 CuSO4
he transition metal ion to the surrounding molecules or ions.2SO2(g) O2(g) 2SO3(g)
ember this one.
remember thisThese
one. Theseare a are a +3 +3 +3 +3 +3
small polar molecules attracted to the transition Anmetal
aqueous
An
cationa solution
aqueous
Why is the of
solution vanadium
of
vanadium(V) oxidein
vanadium the
used in +5
in oxidation
the
pellets +5 state
oxidation
rather than as a (either
state (either
d way
goodtowaylearn.to learn. TiCl3 VCl3 CrCl3 Mn(OH)3 Fe2O3
vanadate(V) or dioxovanadium(V))
vanadate(V) can becan
or dioxovanadium(V))
ands. A ligand has an electron pair that it can donate to the single mass? reduced from +5
be reduced to +2
from +5 showing
to +2 showing
ion. Typically two to six ligands may surround a transition
+4 metal +4
b Is +6 +4
all the
lex. The number of ligands surrounding the central oxidation
ionall the
isTiO
called
2
the states
oxidation in
VO22 5 states between.
V O a homogeneous
K2Cr2O7
in MnO
between.
or heterogeneous catalyst in this reaction?
2
tion number. Common ligands that are neutral molecules c What possible advantage could be gained by passing the gas mixture
, H O; ammonia, NH ; and carbon monoxide, CO. These molecules over+5
several beds of catalyst?
+7
eone
26.1
Figure
2
26.1
pairTest
of tubes
Test 3containing
non-bondingtubes containing
electrons with which they can form a V2O5 KMnO4
ons
nd. of dissolved
solutions
Negative of
ions vanadium
dissolved
that vanadium
can be ligands include the chloride ion,
ounds
ecompounds
ion, OH in–;different
and in oxidation
thedifferent
cyanide –
states.
oxidation
ion, CN . states. 3.3 TRANSITION METAL COMPLEXES
The transition elements form ions by losing electrons from both the 4s and the
ouCanidentify
you the oxidation
identify the states?
oxidation states?
PERIODICITY
NAMES OF SOME LIGANDS 3d subshells.

Transition Thisions
metal is possible because these subshells
are characteristically are
small and very close
highly to each
charged. Thisother
in energy.
high You
charge willNrecall
density thatinthe
results an4s subshell
ability is filled attract
to strongly before the 3dand
ions subshell
small
Formula Name O
because
polar
H an
H empty
molecules, 4s subshell
H forming C is lower
H a complex O in energy
ion than
in which the 3d subshell;
coordinate however,
(dative)
:NH3 Ammine- of roughly the same stability in aqueous solution or in crystalline solidsOxidation
when full,
bonds linkelectrons Hare removed
the transition metal from
ion tothe
the4ssurrounding
subshell before by losing
3d. Foror
molecules states of transition metals
this
ions.
PERIODICITY
oxide :CO Carbonyl- different numbers of electrons. This contrasts with the metals in Groups 1 and 537 537
interchange
The ions andtosmall
occur,polar
the energy of the
molecules two subshells
attracted to the must be very
transition close,
metal indeed.
cation
O A ligandChas N
:Cl− Chloro-
2 of theare called
Cl
Periodic ligands.
Table an electron pair that it can donate to the
H for which there is a large jump in ionisation energy after
CHAPTER 3
:CN− Cyano- central metal ion. Typically two to six ligands may surround a transition metal
n :OH− Hydroxo-
the electrons
ion in a in the outer
complex. shellofhave
The number ligandsbeen removed.
surrounding the central ion is called
45 formulae
Variable oxidation states
Figure 3.3.1 Ligands have an electron pair that can be
9.The the coordination number. Common ligands that are neutral molecules
donated towater,
a transition metal cation.
Common oxidation states
PERIODICITYCHAPTER 3
include
H2O: Aqua-
of Hthe O; ammonia,
2 commonNH ; and carbon monoxide, CO. These molecules
oxides of the elements from scandium to
3
have at least one pair of non-bonding electrons with which they can form a
zinc are shown in Figure 15.7 along with the stable oxidation states of each
CHEMISTRY: FOR USE WITHcoordinate
THE IB DIPLOMA PROGRAMME
bond. Negative ions that can be ligands77
include the chloride ion,
Oxidation states and common oxides of the elements scandium to zinc
Cl–; hydroxide ion, OH–; and the cyanide ion, CN–.
element in its compounds. The main oxidation states of the elements are
with the main
shown inTABLE
boldoxidation
blue
3.3.1 OFstates
print.
NAMES in bold blue.
SOME LIGANDS
CHEMISTRY: FOR USE WITH THE IB DIPLOMA PROGRAMME O N 71
Ligand Formula Name
H H C O
Sc
Ammonia Ti :NH3V Cr Mn
Ammine- Fe Co H Ni H
Cu H Zn
Common Sc2monoxide
Carbon O3 Ti2O3 V2O3
:CO Cr2O3 MnO FeO CoO NiO
Carbonyl- Cu2O ZnO
oxides
Chloride ion TiO2 :ClV−2O5 CrO3 MnO 2 Fe2O3 Co2O3
Chloro- Cl CuOO C N
CHAPTER 3
H
Cyanide ion :CN− Mn2O7
Cyano-
Hydroxide ion :OH− Hydroxo-
+7 Figure 3.3.1 Ligands have an electron pair that can be
Water H2O: Aqua- donated to a transition metal cation.
+6 +6
m_536-552.indd 537
QA_Chem_536-552.indd 537 +5 CHEMISTRY: FOR USE WITH THE IB DIPLOMA PROGRAMME
3/27/19 2:10 PM 2:10 PM
3/27/19 77
+4 +4 +4
+3 +3 +3 +3 +3 +3 +3
+2 +2 +2 +2 +2 +2 +2 +2 +2
+1
Figure 15.7 Oxidation states and common oxides of the elements scandium to zinc with
the main oxidation states in bold blue print.
The elements at each end of the series in Figure 15.7 give rise to only one
Bilal Hameedoxidation state. The elements near the middle of the series have the greatest Transition Elements
the +2 Figure 15.8 The oxidation states of
range of oxidation states. Most of the elements form compounds inMarginalizer
Bilal Hameed
state corresponding to the use of both 4s electrons in bonding. vanadium showing the colours of its ions in
the +5, +4, +3 and +2 oxidation states.
The +2 state is a main oxidation state for all elements in the second half of the
20
16
9.46 Shape of d-orbitals

The d-sublevel has 5 orbitals. The shapes of the 3d atomic orbitals that
make up the 3d sub-level are shown in the next slide.
They all have the same energy (in the gas phase ions), but different
orientations in space relative to one another.
Each of them varies in their electron arrangement in space. Four of

them have shapes that look like two p orbitals configured variously
along different planes. While one looks like a p orbital surrounded by an
electron cloud doughnut.

The 3 orbital system is between the axes and 2 orbital system is along
the axes.

They are divided into two types.
The 2-orbital group where the orbitals align along the axes, eg: dx2-y2,
dz2.
And the 3-orbital group, where the orbitals align themselves between
the axes, eg: dyz, dxz, dxy.

21
17

The electron cloud of dx2-y2 is along the axes, while that of dxy is
between the axes.
Rotate
45€
→
Axe y -
'
day Axe y -
'
day
9.50 Complex ions

Metal ions exist in aqueous solution as hydrated ions.
So, Cu2+(aq), Al3+(aq) and Ag+(aq) can be represented more accurately as

[Cu(H2O)6]2+(aq), [Al(H2O)4]3+(aq) and [Ag(H2O)2]+(aq) respectively.
In these ions, the water molecules are bound to the central cation by
co-ordinate (dative covalent) bonds.
25.7 The formation of complex ions
In this section you will learn to: From our studies of enthalpy changes in solution, we know that metal ions
• Describe how complex ions are exist in aqueous solution as hydrated ions. So, Cu2+(aq), Al3+(aq) and Ag+(aq)
formed from ligands can be represented more accurately as [Cu(H2O)6]2+(aq), [Al(H2O)4]3+(aq) and
[Ag(H2O)2]+(aq) respectively. In these ions, the water molecules are bound to
• Find the co-ordination number 9.51 Complex ions
the central cation by co-ordinate (dative covalent) bonds (Figure 25.11).
of a metal ion
H− H H− H
−
O O
H
O H H−
−
H H− O− O Al3+ H
Cu2+ O−
−
O
−
H H
H
−
H− O
−
H
−
DEFINITIONS H −O
O
−
A complex ion is an ion in which H H

H H
−
−
a number of molecules or anions
are bound to a central metal ion
by co-ordinate (dative covalent)
bonds. H− H
O Ag+ O−
A ligand is a molecule or anion
−
H H
bound to the central metal ion
in a complex ion by co-ordinate Fig 25.11 Co-ordinate bonding in hydrated cations
bonding.
Other polar molecules, besides water, can also co-ordinate to metal ions. In excess
The co-ordination number of a ammonia solution, Cu2+ exists as [Cu(NH3)4(H2O)2]2+(aq) and Ag+ exists as
metal ion in a complex ion is the [Ag(NH3)2]+(aq).
number of co-ordinate bonds to it
Bilal Hameed In addition to polar molecules, anions can also form co-ordinate bonds to metal
from surrounding ligands. Transition Elements
Bilal Hameed
ions. For example, when anhydrous copper(II) sulfate is added to concentrated Marginalizer
hydrochloric acid, the solution becomes yellow-green due to the formation of
2–
[CuCl4] ions.
Table 25.5 The hydration energies of some metal
ions Ions such as [Cu(H2O)6]2+, [Cu(NH3)4(H2O)2]2+ and [CuCl4]2–, in which a
22
18
9.52 Complex ions

Other polar molecules, besides water, can also co-ordinate to metal
ions.
In excess ammonia solution, Cu2+ exists as [Cu(NH3)4(H2O)2]2+(aq) and

Ag+ exists as [Ag(NH3)2]+(aq).
In addition to polar molecules, anions can also form co-ordinate bonds

to metal ions. For example, when anhydrous copper(ii) sulfate is added
to concentrated hydrochloric acid, the solution becomes yellow-green
due to the formation of [CuCl4]2– ions.
9.53 Complex ion definition

Ions such as [Cu(H2O)6]2+, [Cu(NH3)4(H2O)2]2+ and [CuCl4]2–, in which a
metal ion is bonded (via dative/coordinate covalent) to a number of
molecules or anions are known as complex ions.
The molecules and anions bonded to the central metal ion are called
ligands.
Each ligand contains at least one atom with a lone pair of electrons.
These can be donated to the central metal ion forming a co-ordinate
bond.
9.54 Complex ion - coordination number

The ligands are said to be co-ordinated to the central metal ion and the
number of ligands in a complex is usually two, four or six.
The number of co-ordinate bonds from ligands to the central metal ion
is described as its co-ordination number.
Water is by far the most common ligand in complex ions.
Transition metal ions have a tendency to form complex ions because

they are small and have a high charge density.

23
19
9.55 Fe2+ complex ion

The structure of [Fe(H2O)6]2+ is shown below. H2O is the ligand in this
complex ion. The shape of this complex ion is octahedral and it is
called the hexaaquairon (II) ion.
H H
H O
H
H O
O
2+
Fe2+ H
Cu
H
O H
O
H
H
O
H H
2+
4 Figure 15.13 Dative
Write the formula for the oxide corresponding to the covalent bonding in
highest an aqueous Cu ion. Each water molecule uses a
expected
lone pair of electrons to form a dative covalent bond with the central metal ion.
oxidation state for:
a Ti Tip
b Ni In aqueous solution, the copper(ii) ion is surrounded by six water molecules to form the
complex ion [Cu(H2O)6]2+. In solid hydrated copper(ii) sulfate (CuSO4.5H2O), however,
c Cr there are only four water molecules co-ordinated with each copper(ii) ion. The fifth
water molecule in the solid copper(ii) sulfate is associated with a sulfate ion, SO42−.
5 Write the half-equation for the conversion of each of the following
transition metals to the different oxidation state.
9.56 Cu complex ion
Other polar molecules, besides water, can form dative covalent bonds
2 3
2+ with metal ions. For example, in excess ammonia solution, Cr3+ ions form
a Fe to Fe 3+ 2+ 2+ +
[Cr(NH3)6] , Cu ions form [Cu(NH3)4(H2O)2] and Ag ions form
b MnO4 to Mn2 [Ag(NH ) ]+. In addition to polar molecules, anions can also associate with
CuSO4(anhydrous) iscations
white,usingbut
3 2
dativewhen
covalent mixed
bonds. For with water,
example, it forms
when anhydrous a
copper(ii)
c VO2 to V3
complex ion with H2O giving the solution a blue color.
sulfate is added to concentrated hydrochloric acid, the solution contains

yellow [CuCl ]2− ions.
6 Describe the role of the platinum–rhodium catalyst in the
4
catalytic
converter of aCuSO
car. Ions such as [Cu(H2O)6]2+, [Cu(NH3)4(H2O)2]2+ and [CuCl4]2− in which
4(anhydrous) a metal ion is associated
[Cu(Hwith
2O)a6number
]2+ (copper sulfate
of molecules or anions solution)
are called Tip
7 complex
In one stage of the industrial production ions, andacid,
of sulfuric the anions and dioxide
sulfur molecules gas
attached to the central metal When anions act as ligands, the overall
ion are called ligands. Each
H ligand must have at least one lone pair of
is oxidized to sulfur trioxide gas in the presence of a Hcatalyst of charge on the complex ion does not
electrons which itHuses to
O form a dative covalent bond with the metal ion. equal the oxidation number of the
vanadium(V) oxide. The catalyst is used The in pellets
number and in
of ligands the gaseous
a complex ion mixture
is typically two, four or six. central metal ion.
is passed over layers, or beds, of catalyst. The equation
H O for this reaction is:H
Chemists have an alternative name for dative covalent bonds which they
2SO2(g) O2(g) 2SO3(g) O
often prefer when describing complex ions. The alternative name is ‘co- Key terms
H
Cu2+
Hordinate
a Why is the vanadium(V) oxide used bond’, which also gives rise to the terms ‘co-ordination compound’
in pellets rather than as a
andO‘co-ordination number’. A co-ordination compound is one that contains A complex ion is an ion in which a
single mass? H
a complex ion, and the co-ordination number of a complex ion is the number of molecules or anions are
O
H
number of co-ordinate bonds bound to a central metal cation by co-
b Is the V2O5 a homogeneous or heterogeneous catalyst in from
thisthe ligands to the central metal ion.
H reaction? ordinate bonds.
O
Co-ordination compounds contain complexes which may be cations, anions
c What possible advantage could be or
gained by passing the gas mixture
neutral molecules H(FigureH15.14). Examples of co-ordination compounds A ligand is a molecule or anion bound
over several beds of catalyst? Figure 15.13 Dative covalent bonding in an aqueous Cu2+ ion. Each water molecule uses a
include: to the central metal ion in a complex
lone pair of electrons to form a dative covalent bond with the central metal ion. ion by co-ordinate bonding.
K 3[Fe(CN)6] containing the negatively charged complex ion [Fe(CN)6]3−
●
The co-ordination number of a metal
Fe(NO3)3.6H2O containing the positively charged complex ion
●
3.3 TRANSITION METAL COMPLEXES Tip[Fe(H2O)6]3+
ion in a complex is the number of co-
ordinate bonds to the metal ion from
● Ni(CO)4 containing a neutral complex between nickel atoms and carbon
In aqueous solution, the copper(ii) ion is surrounded by six water molecules to form the the surrounding ligands.
Transition metal ions are characteristically monoxide
small molecules.
and 2O)highly charged. This
complex ion [Cu(H 2+
6] . In solid hydrated copper( ii) sulfate (CuSO4.5H2O), however,
high charge density results in an ability tothere are only four

strongly water molecules
attract ionsco-ordinated
and small with each copper(ii) ion. The fifth
water molecule in the solid copper(ii) sulfate is associated with a sulfate ion, SO42−. 429
polar molecules, forming a complex ion in which coordinate (dative) 15.6 Formation of complex ions
9.57 Ligands
bonds link the transition metal ion to the surrounding
Other polar molecules,molecules or ions.
besides water, can form dative covalent bonds
3+
The ions and small polar molecules attracted with metal
to the ions. For example,metal
transition in excess ammonia solution, Cr ions form
cation
[Cr(NH3)6]3+, Cu 2+ ions form [Cu(NH ) (H O) ]2+ and Ag+ ions form
A ligand has
are called ligands.Common ligands that
an electron are3)2neutral
pair that
469983_15_Chem_Y1-2_418-449.indd
[Ag(NH + it
429
molecules
can
] . In addition donate to include
the
3 4
to polar molecules, anions water,
2 2
H2O;with
can also associate
13/04/19 10:03 PM
central metal ion. Typically two to six ligandscations may surround

using dative covalentabonds.
transition metal
For example, when anhydrous copper(ii)
ammonia, NH 3; andsulfatecarbon
ion in a complex. The number of ligands surrounding
monoxide,
is added to theconcentrated
CO.
central ion
These molecules have at
is calledacid, the solution contains
hydrochloric
the coordinationleast one Common
number. pair of non-bonding
yellow [CuCl
ligands that4are ]2−electrons
ions. with which they can form a
neutral molecules
include water, H2O; ammonia, NH ]2+, [Cu(NH 2+ and [CuCl ]2− in which
3; and
carbon
Ions suchmonoxide,
as [Cu(H2O)6CO. These3)molecules
4(H 2O)2]
coordinate bond. 4
a metal ion is associated with a number of molecules or anions are called Tip
complex ions, and the anions and molecules attached to the central metal When anions act as ligands, the overall
coordinate bond. Negative ions that can be ligands include the chloride ion,
– Negative
– ions that can be
ion are
Cl ; hydroxide ion, OH ; and the cyanide electrons
ligands
called
ion, CNwhich –
ligands.include
Each ligandthe chloride
must ion,
have at least one Cl —;pair of
lone charge on the complex ion does not
. it uses to form a dative covalent bond with the metal ion. equal the oxidation number of the
hydroxide ion, OH—The
; and theofcyanide
number ion, CN
ligands in a complex .
—typically
ion is two, four or six. central metal ion.
PERIODICITY
TABLE 3.3.1 NAMES OF SOME LIGANDSChemists have an alternative name for dative covalent bonds which they
Ligand Formula oftenName N
prefer when describing complex ions.OThe alternative name is ‘co- Key terms
ordinate bond’, which also gives rise to the
H terms ‘co-ordination
H H compound’
H C O
Ammonia :NH3 Ammine- number’. A co-ordination compound is one that
and ‘co-ordination H contains
A complex ion is an ion in which a
a complex ion, and the co-ordination number of a complex ion is the number of molecules or anions are
Carbon monoxide :CO Carbonyl- bound to a central metal cation by co-
number of co-ordinate bonds from the ligands to the central metal ion.
O ordinate bonds.
Chloride ion :Cl− Chloro- compounds contain complexesClwhich may be cations, anions C N
CHAPTER 3
Co-ordination H A ligand is a molecule or anion bound

Cyanide ion :CN− or neutral
Cyano-molecules (Figure 15.14). Examples of co-ordination compounds
to the central metal ion in a complex
include:
Hydroxide ion :OH− ●
Hydroxo-
K 3[Fe(CN)6] containing the negativelyFigure Ligands have
3.3.1complex
charged ion an electron6]pair
[Fe(CN) 3− that can be
ion by co-ordinate bonding.
donated to a transition metal cation. The co-ordination number of a metal

Water H2O: ● Aqua-
Fe(NO 3)3.6H 2O containing the positively charged complex ion
ion in a complex is the number of co-
[Fe(H2O)6]3+
ordinate bonds to the metal ion from
Ni(CO) containing
CHEMISTRY: a neutral complex between nickel atoms and carbon
FOR USE WITH THE IB DIPLOMA PROGRAMMEthe surrounding ligands. 77
●
4
monoxide molecules.
15.6 Formation of complex ions 429
The ions and small polar molecules attracted to the transition metal cation
are called ligands. A ligand has an electron pair that it can donate to the
central metal ion. Typically two to six ligands may surround a transition metal
ion in a complex. The24number of ligands surrounding the central ion is called
the coordination number. Common 20 ligands that are neutral molecules
include water, H2O; ammonia, NH3; and carbon monoxide, CO. These molecules
coordinate bond. Negative ions that can be ligands include the chloride ion,
Cl–; hydroxide ion, OH–; and the cyanide ion, CN–.
9.58 Ligands
TABLE 3.3.1 NAMES OF SOME LIGANDS
Ligand Formula Name O N
H H H
Ammonia :NH3 Ammine- H
Carbon monoxide :CO Carbonyl-
O
Chloride ion :Cl− Chloro- Cl
H
Cyanide ion :CN− Cyano-
Hydroxide ion :OH− Hydroxo- Figure 3.3.1 Ligands have an ele
Water H2O: Aqua- donated to a transition metal ca
CHEMISTRY: FOR USE WITH THE IB DIPLOMA PRO
9.59 Ligands
Ligands are Lewis bases having lone pairs.They bond to the transition
metal ion to form a complex ion.
Six, four or two ligands combine with one metal ion, so the formation of
a complex ion may be represented as the donation of six or four or two
pairs of electrons to the metal ion.
A dative covalent bond (co-ordinate bond) is formed between each

ligand and the metal ion.
9.60 Oxidation state of complex ions

The oxidation number of a transition metal in a complex ion may be
worked out from the charges on the ligands. Ligands may be either
neutral or negatively charged.
In [Fe(H2O)6]2+ all the ligands are neutral. The overall charge on the ion is
just due to the Fe, so the oxidation number of Fe must be +2.
In [CuCl4]2— all the ligands have a 1− charge, so the total charge on all
four ligands is 4−. The overall charge on the ion is 2−; therefore, the
oxidation state of Cu must be +2.

25
21
9.61 Shapes of complex ions

The type and number of ligands surrounding the central metal ion is
indicated in the name of the complex.
The shape of the complex ion depends on the number of ligands

surrounding the cation.
These geometrical shapes are the same as those assumed by

molecules with 2 to 6 atoms (and no non-bonding electrons)
surrounding them.

The most common coordination numbers are four and six, although
some complexes have only two ligands.
According to VSEPR theory, the coordinate bonds take on the

geometric arrangement that gives the complex the lowest energy.
The shape of a complex with two ligands is linear, with four ligands it
may be tetrahedral or square planar, and with six ligands the complex is
octahedral.

These complexes do not always obey VSEPR theory rules, so although
six coordinate complexes are virtually always octahedral, four
coordinate complexes may be tetrahedral or square planar.
Silver ions often only form complexes with two ligands. This can be
explained by the larger size and single positive charge of the Ag+.

revise entropy.
mistry of complex ions

Shapes of[Cu(H
complex You 3+will learn more NH3 about Aldehydes reduce
6] ions
electron structures of manganese, iron andO)
their2+
respective 2+ and 3+ ions Cl–
esented
2COOH
more accurately as 2 (aq), iron
[Al(H and
2O)so4] destroy
(aq) andhaemoglobin’s oxygen-carrying breathle
A few complexesCl– o
+
(aq) respectively. In these ions, the water molecules using
are bound Tollens’
to reagent to
Cl–
test Cu +
Cl–
ketones do not. Th
be loss 2o+
e3+ each have
The shape
half-filled
of a
3dion
complex
orbitals.
ion
This
depends
makes capacity.
on the ThisCstable
number
themof25.11).
more
ofexplains the poisonous
ligands around the
C effect of carbongeometry (Figure
bin
cation by co-ordinate
central (dative
metal covalent) bonds
(the co-ordination (Figure
number for
the aldehydes
central metal andion). ketones in
Complexes with a tube, giving thebe
Ptna
2+
and Fe , respectively. Hence, H3N in manganese the monoxide,
Complexes+2with N iswhich
–a 26
state moreis a better ligand
22
than N oxygen.
co-ordination
–
number Carbon may t
+3, whereas in In complex
iron the ions
+3 with
state co-ordination
is more number:
co-ordination
stable than Topic
number
+2. of 26.2, Reactions of the Some
Cl– complexes a
H− H atom acting as
h nitrogen faulty gas 6heaters.
are monoxide
H
usually
− Because
H is often
octahedral NHformed
it binds3 morebystrongly
incomplete
of
to thecombustion
2 are usually linear
in
Complex iron(II)
ions
Figure may s 7 group A square planar complex
NH
and the bond ▲ carbonyl in aldehydes and
−
● 6 – the shape is octahedral 2+
−
3
angles are all 90° Co A few complexes with
Cr + 3
Cl–
plex protein
elements
NS
O called globin. iron than oxygen, Oit is possible to suffocate in a room with a co-ordination numbe
nHmolecule asHaNligand.
● 4 – the shape is sometimes tetrahedral, bond
also a number of complex plentiful oxygen.
ions
ketones.
angle 109° 5’ but there are Representing of 4 are planar th
2+ with a co-ordination– number of 4 –that
3
the electron structures of Cu,
Hsquare planar, bondH− Cu +
and 9. Cu64 NH Shapes
using the ofSynoptic
complex
‘electrons-in- Cl link
ions A solution
Representing contain
thre
25.9
Cl –
is not
O a very goodare ligand, angle 90° . 3 Cl
−
−
’ notation. O Anaemia is a condition which may be caused
O Al 3+
H by a with a is used
diagrams in this to in organic
e easily 2+
Cugiven up ● to2−cells.
– the shape is linear with bond angle 180°. O − Cl–NH
Heading
The structure A of complex
You will learn ions
more
Complexes
about
−
hich oxidation state would
H you shortage expect H copper to be more
of haemoglobin.MThe body suffers from stable, co-ordination a number Pt + of Aldehydes reduce 2 3
HThe structures visualise the shape
−
O Complexes with a
−
are illustrated in Figure 6.7. H 4 areM
+2?
ond irreversibly to the
co-ordination number of
lack of oxygen and the using
symptoms Tollens’ reagent
include Cl – to test
fatigue,
usually tetrahedral
ketones do not. Th
−
experience H 6 are usually

you will know octahedral that copper NH Figure
compounds − O6.7 Theusually shapes of exist complex
3
in ions. shape is to use we
s state.
oxygen-carrying
O will learn breathlessness, and a for pale aldehydes
Co skinnumber
+
colour. andThe ketones
causes inmay 2 NH tube, giving the na
−
H of ligands, but there of the paper and d
Cl– and A few complexes with 3
2
tion NH What
you factors to:mightThe increase formulathe of arelative complex stability
Hion tells of
usthe
octahedral the +2 type
tetrahedral
nous
over Heffect
the +1 Hofof
3
carbon
state for copper? are nobe loss of rules
definitive bloodrelating or deficiency Topic
the formula 26.2,of iron ofReactionsin theAn
a complex
a ofarethe
co-ordination
ofdiet.
ion toThe
number
latter
its structure,
−
Chemistry of complex ions

omplex
the shapes
dnthan oxygen.
ions
complex
Carbon i.e. the arrangement– of ligands
may be treated by Cl taking
– carbonyl
aroundCu ‘iron’
+ the Cl group
–central in
tablets metal
whichaldehydes
and
4octahedral
ion.
contain
planar
However:
tetrahedral and
complex is saidComplex
complexes show
to show six-fold
Isomerism
four-fold
ions
in may
co-ordin
tra
co-ordination
20.7, we found that E values could be used Cl to predict the
mplete
the
d ofeffect
redox combustion
water as a in • complex
ofreactions.
H − iron(II) ionssulfate.
H
with a co-ordination Complexes ketones.
M with
number of–six usually have ligands in
a a Most complexes are formed by Representing
You ions.haveHowever, met th
it is isom
also
n the complex Shapes ion of complex octahedral ions positions
− so Complexes
that the
co-ordination
with
six electron
number
Cl around
pairs M central ion are
the
a complex using the uncharged with metalthe atom. same mo
For exampl
h of the M3+(aq)/M2+(aq) O systems Ag+ inasOFigure
repelled far 25.9 co-ordination
will2 are oxidise number the of Representing thre
how polydentate The shape ligands
of a complex ion depends onapart the number as possible
4 areofusually of ligands (Figure
usually
tetrahedral linear
around 25.12), the chromium all form a complex with carbon monoxide. Th
m: square-planar linear in 6.8. of their atoms into s
−
he central metal NH
central metalHion (the
cation •co-ordination
complex ions 3 Hwith aofco-ordination
number the central metal number ion). of four usually are illustratedhave ligands in Figure diagrams in this
Cr + 3 Figure 6.7 The − shapes of complex ions.
use →
aq) Br2 (aq)
of diagrams
In complexinhow
+ions2e with E =co-ordination
–1.09
tetrahedral V positions,
number:
although a few four co-ordinated complexes, such as
▲ Figure
M 8 The four main shapes 369
of geometrical
visualise theisome shape
ordinate bonding hydrated
2+
cations
[PtCl 3+ ] 2–
have − a square planar structure (Figure 25.12), M
ncecisEand trans of
values M (aq) → M– 4(aq) + e for the systems in
isomers
shape is to use we
● 6 NH– the shape is octahedral Cl
•ofcomplexes and the with bond angles
a co-ordination aretransition
all 90°
Cl– number by: of
metal twocomplexes
usually
to show have usinga linear wedge square Geometrical isom
e 25.9.
molecules, Then decide
besides 3
which
water, can these
also systems
co-ordinate toAn
could metaloctahedral
be oxidisedions. complex
In excess is said six-fold co-ordination; planar
●2+4 exists
–
+ the shape –is sometimes arrangement 2+ of ligands
tetrahedral, bond angle+ and
(Figure
and tetrahedral 109° dotted
25.12).
octahedral complexes
5’ but bonds
there show
are four-fold
tetrahedral co-ordination. of the paper and d
2–
lution, Cu
7 (aq) + 14H (aq) + 6e →
as [Cu(NH )
3 2Cr (H
4 2 (aq)
3+O) ] (aq)
2 + 7H2O(l) for which and Ag exists as Here ligands differ
(aq). V. also a number of complex ions with a co-ordination Most complexes number are+offormed
Pt 4 thatNH by ions. However, it is also possible to form 2 3
+1.33
CN– are square planar, bond angle 90°9.65 . – Linear a complex using the uncharged metal atom. For example, nickel, This Isomerism
iron and type of isome in tra
f
to
l polar
NH molecules, anions
● 2 – the shape is linear with
3
can
+
Cl
also
–
form
bond angle 180°.
Cl
co-ordinate chromium Hint
bonds
all
Cl– in
form to a metal
complex with carbon monoxide. The three square
You have met com
complexes planar isom
ample, when anhydrous copper( Co ) sulfate
If the is
complex added
are 2
to
contains
illustrated concentrated
two
M ligands
Figure NH
6.8. (co-ordination number 2), it is
II A few complexes with M 3
complex the ion [CrCl
– –
NC The structures are illustrated in Figure 6.7. Cl
c acid, the solutionCN becomes
– yellow-green linear; due examples to the
a co-ordination Allnumber
areformation
the six
CuClligand 2− and of [Ag(NH positions
Cl– 3)2]+ ions. in an with same mo
ns. Fe3+ of 4 are planar Pt2+
octahedral complex are
square-planar linearequivalent may
of theirbe next atoms toin eacs
2+ –
Cl – Co Cl
or on opposite side
s [Cu(H2O)6]2+
3 , [Cu(NH3)4(H2O)2]2+ and [CuCl4]2–, in ▲whichas are aall
Figure 8Cl–the Thepositions
four mainin the other
shapes of geometrical isome
CN– Cl
Complexes
–
with a –
Cl or anions are known as ion (the trans- or E
associated with a number of molecules three geometries.
+ transition metal complexes using + wedge
–
ons. The molecules
4 are and usuallyanions tetrahedral bonded to the central metal ionCl
Cl–
Cu Cl – H 3 N Ag NH 3 Geometrical 123 isom
gands.– Each ligand contains at least one atom with and
a lone dotted
pair bonds
ofelectrons is called a In the square
Here ligands differ plana
complexCN ions. Key terms The ion Complexes
making the with
attachment avia a lone pair of
– −
Cl ligands type ofmay be
hese can be donated to Cl ligand. The resulting ion is called a complex ion.
isthe central or anion metal The ion ion making forming
co-ordinationthe attachment
Ais few
a co-ordinate
number via a lone pair of electrons is called a
This isome
with complexes with a Complexes with a
Synoptic and numberlink co-ordination number
A ligand
Key terms a molecule
An example of a complex ion ion water as a ligand
ion. is [Cu(H O) ] (Figure 6.4).
2+
of 2 are usually linear
Hint
ligand. The resulting called a complex
gands
es with a are said to be
co-ordination thatco-ordinated
has at
Complexes
Aofligand
least
is a and
one
molecule witha a to
lone
bondsortoanion
pair the central metal
co-ordination ion
co-ordination
2
or Z- form)
6
or com
on o
NH
of 6 have in 3 electrons An example of a complex ion with water as a ligand is [Cu(H O) ] (Figure 6.4).
of 4 have a square 469 planar
2+
mber
of ligands an a complex number
that hasmetal
An octahedral is
at least
usually
one aof
complexlone 4pair
usually
ortwo,
is have
said four to or
show six.
six-foldThe number
co-ordination; square planar of 2 have a
H H 2 6
central ion by dative The shap
dral arrangement of and co-ordinate
ateligands.
bonds from ligands
of a tetrahedral
electrons
tetrahedral
to
metalthe
and
bond. bonds to
complexes arrangement
a
show four-fold co-ordination. square-planar
You will itslearn more about
H O
linear arrangement
cisplatin chromium
complex ionion (the
[CrCl
ofcentral
ligands. metal ion is described as of H H
A central
co-ordinate ion by
bond is aa dative
dative or
arrangementAll six ligand ligands. positions
16.9 in an
ofshapes
ligands.
geometrical
may be nextisomer
H O
co-ordinate bond. OH The of complex ions
ion number. Most in isTopic
H
The ion 30.3, making the The action loneofpairanti-

structure
NH of complex ions ligand
covalent bond formed between the
complexes
A co-ordinate
and –thebond
Clbond central is are
ametal
dative formed
ion. by ions. However, –
it
octahedral
also possible H to
complex
form
The
attachment
O
shapes
are equivalent
viaofa complex ions depend onisthe
of electrons
O H
number
called a of ligands around the
to eac
Key terms Cl
3 covalent
a complex
A complex ion using formed
is an ionthe between
in which the
uncharged metal atom. For example,
or anioncancer
ligand. The nickel,
resultingiron
central metal ion.
and a complex
ion is called Cu2+ There is
ion.
no simple, definitive rule
properties.
for predicting the shapes
or on opposite side For exa
far the most common ligand inor complex ions. molecule The strengths of drugs.
H H
ligand and the central metal ion. of complexes from their formulae, but:
least one lone pair as are all the positionsin complexesin
as athe isother
a number of molecules anions A ligand O
chromium
Aare alla iscentral
form in a
an ioncation whichcomplex withis acarbon monoxide.An The example O
three complexes
of a complex ion Cu2+
with water with ligand H
[Cu(H O) ] (Figure 6.4). 2+
occupy octahedral positions so that the six electron most successful

trans- oranE
complex ion
nate bonds between water
bound to Aqueous
molecules by complex
and that has ations
different metal ions can H
NH a co-ordination
O number of six, the ligands usually
H ● 2 6
a number
are illustrated
co-ordinate ofbonds.
molecules
in Figure or anions
6.8. of electrons and bonds toPt a + H O 2 H
3
ion (the
pairs around the
d using their enthalpy are bound to a central cation by
changes
co-ordinate bonds.
of
In aqueous– solution, hydration central metal (hydration
ion by a dative or three
energies)
transition metal ions generally inexist geometries.
H
central atom are repelled as far as possible.
O
complexesas withoctahedral
O H
a co-ordinationcomplexnumber of four, the trans-isomer
H
ligands usually
● O
H
has no
Cl co-ordinate bond. H H H
udied in Section 5.15. Hydration ions withenergies the9.formula
A66 relateOctahedral
bondto the complex
process: - [Cr(NH ) ]
occupy
3+ tetrahedral H
2+ 3+positions, although there are a few complexes with
co-ordinate [M(H 2 O)
is a dative 6 ] (aq) or [M(H 2 O) 6]
fourfold
Figure 6.4 The [Cu(H2O)6]2+ ion. (aq).
O
3 6 However,
co-ordination, such as the
[Pt(NH ) Cl ], Hwith In the square plana
a square planar
370
O H 3 2 2
H H
x+ Co + high charge – density
A
covalent bond formed between the
few
2
x+ on
complexes the metalcentral
with
NH draws electrons
cation structure. in the O–H bonds
3
− ligands
M (g) + nH2O(l) of → the [M(H
Cl
water2ComplexesO)A
na ]range(aq)
ligand
range
molecules
and
of the
complex central
ions
with
istowards
can
awhich
ion.
be formed
co-ordination
itself.
with
This
a variety of
number
central in
Figure 6.4 The [Cu(H2O)6]2+ ion.complexes
cations
ofa effect
6 have
with
anwith
a co-ordination
octahedral
number of two,
Clligands
the usually form
●
may be O
is anpolarising causes thesome of the
Synoptic to link
aA co-ordination number linear structure central metal ion. Cu2+
2. 36
complex ion an ion in
Shapes of Complex Ions
and of surrounding ligands. Ammonia effective ligand and, for H H
A range offorms
complex ions or can be formed with a variety of central cations
on energies of some cations complexed
are listedwater arrangement
of
in
and
a number
example,
4Table
are a bound
range
of molecules
molecules
are planar the
of a25.5.
to
of ligands.
complex
surrounding to anions
Use
central cation
[Cr(NH
dissociate
by this
ligands.
) ]
Ammonia
(Figure
table
6.5).
isproducing
an effective ligand
+
Hand,ions.
These structures
for
are all illustrated
3 6
3+
in Figure
O 16.17.
or Z- form) or on o O
H
example, forms the complex [Cr(NH ) ] (Figure 6.5).

123
3+
– 3 36 H
stion Cl7. co-ordinate bonds.
chromium ion (the NH3
NH
3+ 2+ +
[Fe(H2O)6] (aq) + H2O(l) [Fe(H2O)5OH] (aq) + H 3O (aq)
You will learn more about cisplatinNH3
O
H
Cl– Cu+ C
Complexes with a This explains Cl –
why the aqueous solutions of most transition metal compounds geometrical isomerH H
of as CuSO , FeCl , Co(NO ) in Topic 30.3, The actionacidic. of anti-

H3N Figure 6.4 The [Cu(H2O)6] ion. 2+
Complexes with a
co-ordination numbersuch and CrCl are moderately H3N co-ordination numb
A range of complex ions can be formed with a variety of central cations properties. For exa
4 3 3 2 3 H3N of 2 are usually line
4 are usually tetrahedral
In oxidation states higher than
cancer
3+, the
drugs.
and a range
polarising of surrounding ligands. Ammonia is an effective ligand and, for
power of) the central
Cr3+
metal
NH3
Cr3+
NH3
ions. example, forms the complex [Cr(NH ] (Figure 6.5). NH3 most successful an 3+
ion is even greater. This causes a release of even more H+ ions and the loss of
3 6
H3N Cr3+ H3N
water molecules resulting in oxyanions. For example, neither [Cr(H2O)6]6+

Cl– H 3N NH3 trans-isomer has no NH3 NH3 Cl– Cl–
analysis
7+
An octahedral complex nor
Cl
is [Mn(H O)6] six-fold
said to 2show exist co-ordination;
in aqueous solution.
– NH
square planar Instead, the loss of two water 3
Pt2+
Complexes with a
370
analysis
+ H N
molecules and eight
and tetrahedral complexes show four-fold co-ordination. NH H ions from each of these ions results
co-ordination
in theNHformation of
number of Cl– 3
and qualitative
6 are usually octahedral 3 3

2– – +
CrO4 and MnO respectively.
6.5 The
Figure 4 [Cr(NH ) ] ion. NH
3+ Cr
Cl–
3
A few complexes with
and qualitative
NH
Most complexes are formed by ions. However, it is also possible to form
3 6
Cu 2+
–
3
3+
3 a co-ordination number
Cl Cr
6+ of 4 are planar
ligands is ‘ammine’ with two letter+‘m’s in
Figure 6.5 The
used[Cr(NH ) ] ammonia
ion.
→ + 8H (aq) + CrO42–(aq)
3+
The word for the
a complex using the uncharged Cu metal [Cr(H
Cl the atom.
name. TheFor 2 O)example,
[Cr(NH 6]) ] ion (aq) nickel,
2+
is called H2H
N
a hexaammine 2O(l)
iron and
chromium(III) ion.
–
3 6
Cl– 3+ 3
Cl – 3 6
The word used for the ammonia ligands is ‘ammine’
a –NH group.letter+ ‘m’s in
with two
chromium all form a complex with carbon monoxide.
Do not confuse this with7+ The
amine, which
→threeindicatescomplexes –
elements
the[Mn(H Cl–
O)
name. The [Cr(NHCl
as 2chloride
– 6]) ] (aq)ion is called 2H asO(l)
a hexaammine
behave2
+and
8H
chromium( III)(aq)
ion. + MnO (aq) Complexes with a
NH –
4 3 6
3+
2
3
are illustrated
Cl
in Figure 6.8. Anions
Do not such this withions, Cl , which
can also ligands can form
nd qualitative analysis
−
confuse amine, indicates a –NH group.
elements

4 are usually tetrahedral 2
complex ions such as [CuCl ] . 4
2−
Anions such as chloride ions, Cl , can also behave as ligands and can form −
Marginalizer –
Bilal Hameed
6 Transition
Cl The overall charge of a complex ion is always the sum of the individual
complex ions such as [CuCl ] . NH
2−
Figure 6.6 The [CuCl ] ion. 4
2− 4
charges of the ions and molecules from which the complex is made. TypesSo,of ligand 3 Figure 16.17!
Cl–
Transition
The overall The shapes of com

in this case, charge
the netofcharge
a complex
is 2- ion is always
because Figure
the theThe
6.5 sum
complex of the
[Cr(NH
ion ) ]3+individual
contains
3 6
Most
ion. aligands
Cu 2+ use only one lone pair of electrons to form a co-ordinate bond
Figure 6.6 The [CuCl4] ion.
2−
chargesanion
of theand 2+
ionsfour
and molecules Clfrom which (Figure
the complex
Key term central Cu
surrounding Cl– − cations 6.6). is made.
with theSo,central metal ion. These ligands are described as monodentate
in this case, the net charge is 2- because Thetheword
complex ion the
used for because
contains
ammoniaa Cu they
2+
haveisonly
ligands ‘one tooth’
‘ammine’ with to hold
two onto‘m’s
letter the in
central cation (dens is
er
The co-ordination number of a The Cl −

ion has, in fact, four separate
central anion and four surrounding Cl cations−lone pairs of electrons and
the name.(Figure [Cr(NH )Latin
The 6.6). one ofistooth).
] ionfor
3+
called Examples of monodentate
a hexaammine III) ion.include H O, NH , Cl ,
chromium(ligands −
xtreme pain. Figure
Mnthe25.6
2+
[Ar]causing extreme
kidney, CH2 pain. CH2
25 T
elements 2+ CH 2 CH 2
EDTA is usually coordinate
used in bonds alkaline to the buffered solution EDTA to is
ensure usually it is used
the in
anion alkaline buffered solution to ensu
HSo 2 Oeven 3+ though
Mn 2+ Co[Ar] ion must form 2+ water, H 2H N 2 inO, has 2+
two lone pairs H 2ofO electrons, 2+
both H 2 N
2+
form.
Figure Co All
occur on 25.7thethe acid
theoxygen COOHatom
orientation groups
shown,
H 2 N
so itlose would theirbe hydrogenimpossible form. ions
Figure All
25.7for theto these acid COOH
form the
twoanion H 2 N
groups lose their hydrogen ions
y stones, are formed 27
25.7
4−. EDTA 4−
anedioate (calcium
EDTA lone
Co pairs toformingformantwo octahedral coordinate
Co 23 bonds toisEven the Co 2+., whereas the twoCo
Co
Even if the coordination
shaped
[Ar] complex ion number of a complex 4 or if2, the water coordination can only number of a complex is 4 or 2, w
ate on the inner 514
lone
Fe
pairs The formation of complex ions
of 1,2-diaminoethane are
The separated
six lone pairs ever areand shown
act soas it can actsH as of a ligand Theto six lone pairs are of shown
dney. As they grow
ever
−
OOC–H act2as C a monodentate H H ligand
CH2–COO due − to the position −
OOC–H of 2the C alone monodentateHpairs CH2–COO due − the position the
Figure 25.6
bidentate ligand. on the diagram. These form on the diagram. These form
e flow of urine out of Figure 25.7N electrons. Fe 2+
[Ar]
coordinate bonds electrons. with the coordinate bonds with the
C C N Figure 25.14 Figure shows 25.7three N Cexamples C N of octahedral Figure
ions. 25.14 shows
g extreme
ionKey youterms pain.
will learn to:
So even
From The
though
our studies
water,
of enthalpy
H 2 O, changes
has CH two
in 2 central lone
solution,
pairs
metal
we know
ion. of electrons,
This
that
makes both
metal ions
central metal ion. This make
− 9.67
theOctahedral complex a-EDTA[Cu(H 2+ 2O) ]OOC–H
3+ion making the attachment via a lone pair of electrons is called a
Fe [Ar] 2+and 3+
Even existif
Multidentate
occur on
OOC–H
Hin
the
2C
ligand.aqueous coordination
The oxygen Hligands
solution
resulting Hionatom number
isascalled so
hydratedCH it–COO
a 2complex would of−CH
ions. ion.
2complex
So, be multidentate
Cuimpossible (aq), Even
isMultidentate
6−4
Al 3+or
(aq) iffor
2,the Cwater
2and these coordination
Ag + can
(aq) ligands
two
H onlyH NHnumber CH2–COO 2+ of− aEDTA complex multidentate is 4 or and2, 3+ w
2+
ones,
ow complex
A
are isformeda
ions are
molecule or anion Fig 25.10 2 O ion making
The The electron the attachment
structures of
H
via
manganese, 2aNlone pairhexadentate
iron of
and electrons
their 2+ H 2isOcalled
respective 2+a and 3+ 3+
ions 3 hexadentate H2O
ligand
Key terms ever
lone
Ligands act
canpairs beAn as toa+The
represented
that monodentate
form2+
form more
two accurately
coordinate ligand asasHdue
[Cu(H
a2bonds to 2+
O) theto ] the position
(aq), ever
Co [Al(H
]2+Ligands 2+act ,of2O) whereas as
the ] a(aq)
that lonemonodentate
orand
form the pairs two
3Nmany
of coordinate ligand due bonds toHthe O position
to a metal NH32of the ato
om ligands
amany coordinate Nion.bonds 2 to 6 a metal atom ion are
dioate example of a complex ion ion with water ligand 2isH[Cu(H O) (Figure 6.4).
that(calcium
6 4 OH
has at least one lone pair Complexes ligand. resulting
with co-ordination is called a complex number of 2O 6 have an OH octahedral H NH3 2N
Figure
[Ag(H 25.9
O) ] (aq) respectively. In these ions, the water molecules Figure
electrons.
2
25.9
are bound to 3
n the A
o-ordinationligand
inner is a molecule
and bonds to alone
number or electrons.
anion
called pairs 2
of
2
1,2-diaminoethane are separated Fe and
called so it can
multidentate
25.11). ligandligands.acts as a Co An example of a multiden Fe
Cu
CoAn example 2of6 a multidentate is
2+ An example
of electrons
that hasmetal at least
Mn
the multidentate
arrangement
centraland
Co3+ cation
Fe 3+ of a complex ion with water as
each
ofby have
ligands. Hligands.
co-ordinate half-filledH (dative 3d aorbitals.
ligand
covalent) bonds is This
[Cu(H O)makes ]2+
(Figure
(Figure them 6.4). more stable
iononeby alone pair
.ion
Ascentral
they
of grow
electrons and bonds
dative
to TIP
Figure
or than 4−
bidentate ligand.
a EDTA Mn 25.14
. andshows Fe2+, respectively.
H
three O examples Hence, inofmanganese octahedral
H2O TIP
the
EDTAFigure
4−
OH ions.
+22state 4−25.14 . is more shows H3N three NH examples
3 of octahedral
H32N O OH
NHions.
4− can form
2
3
w of
co-ordinate bond.
urine out of
A co-ordinate bond is a dativeMultidentate
central metal ion by a dative Six lone
stable
Remember that
or than pairs +3, whereas are shown
the ligands
H−ligands H
Hin iron on H the the +3 diagram.
state is more EDTA H stable
2 O Sixthan
Remember can
Multidentate
H− H lone +2. form pairs six are
thatligands the shown
coordinate ligandsNH 3 on the diagram. EDTAH 2 O
H 3+ OH O 2+ 2+
3+ 2+
−
CH
−
treme pain.
co-ordinate
covalent bondbond. formed between bonds
EDTA
attached
the is
H with
Oanto the
abbreviation
a central
wedge-shaped
O metalfor ion and
ethylenediaminetetraacetic
bond 2
NH
H so as wellEDTA bonds
asObeing
attached is
H with an
acid.
O described
to a the
abbreviation
The central
wedge-shaped as metal
structure for bondionNH and so as well as being
ethylenediaminetetraacetic H2ac Od
Aligand
co-ordinate
and thebond is ametal
dative Ligands The transition
U E S Tthat
QFigure
2
I25.7
O NOH
elements
form
S H Omany coordinate CH 2 3 bonds [Fe(H to O)aLigandsmetal
] 2+
2 thatpairform
atom or ion many
[Co(NH are )coordinate
] 2+
3 bonds[Cu(NH [Fe(Hto ) O)a 62metal
(H ]
O)2+ ] 2+ ato
A covalent
complexbond
central
ion isformed
an ionbetween
multidentate,
ion.
of
are EDTA
H
Hthe22O
This coming
O Key
is isimportant
termsoutit2ofisinthe
given also Figure screen
asligands. thedescribed
CuH 2+2 N25.8.
H N
coordinate
3 OThe as hexadentate.
H ion NH
making
bonds 3 the attachment
must
2 of multidentate,
are 6 EDTA
H
form2coming
3 ON via a
in iscertain
lone given
outNH
OH it32ofisinorientations
of also
the
electrons Figure isdescribed
screen called
3 6 H25.8.
3a N as hexadentate.
NH 3 3 2
4 H 32N
ionacalled An Co example of a multiden
called 5 a Hmultidentate 2+ H An CoHexample resultingof is multidentate
thea multidentate ion.ligand ligands.
is
in which
METALS METALS
ligand. 2+The called complex

aligand andofthe central metal oraround
ion. paper Fetowards
Write the electron you. structures
Those H H2ofNOCu, Cu+Figure and H −Cu 25.14
2+
using
or paper Fetowards
Cu
‘electrons-in- you. Those Figure 25.14 Cu
Even if the coordination number of a complex is 4 or 2, water can only
25.9
number molecules or anions A
4−boxes’ Othe central ion.
ligand is O a molecule or anion 4−. as a ligand is [Cu(H O) ]2+ (Figure 6.4).
EDTA .
H thatTIP EDTA
−
H O H −
notation.
OH Cu2+ H N HAn example NH of a complex ion H with 3+
O
N water OH
NH H N NH H N
Aarecomplex ion is an ion in which H O−are O Al H
bound to a central cationattached
molecules or anionsever
by 2
act to has
asa at dashed
2
least2+
Cu one
aoxidation
Hmonodentate H bond
lone pair 3O
ligand NH3due
Heading
The structure
A
H
of complex ions
3
Theto the position
6-coordinated attached 2
3
of to Othe
Ocopper(II)
−a dashed 2
3
lone pairs bond
2
complexes
6
ofCH are are
3
NHactually
3
The 6-coordinated
distorted octah
3
H2Oc
−
a number ofbonds. Cob HH2In OOwhich a Co H22C H H
−
the co-ordinate
ligands HOOC–H 2Cof O
Remember
electrons and bonds that
tostate CHthe H2–COOH
would ligands
H you expect H copper HOOC–H
to be more stable, 2–COOH 3
behind the plane of the screen
H O Hor H behind the plane of the screen or
−
are bound to a central cationEDTA by
electrons. is − an abbreviation
2+ O
coordinate for bonds ethylenediaminetetraacetic
to the EDTA H
is an
acid. abbreviation
The structure for ethylenediaminetetraacetic aco
−
dge-shaped bond
HH+1 or +2?
central
attached
metal ion by
to
a dative O
2+ a wedge-shaped bond H
or complexes Oas the top and H bottom ligands are further complexes away than as thethe top
−
co-ordinate bonds.
paper. The two ligands attached paper. The two ligands attached
25 TRANSITION
N C Co C ion N must form in N C C N

of This EDTA isimportant
O)given in Figure 25.8. −of EDTA )2is given inorientations
Figure when 25.8.
co-ordinate bond. O [Cu(NH 3)6] These ligands are 3of
H H
S
f the screen
c[Fe(H
Co
From
isco-ordinate
A 2
are
] 2+
6experience
coming the
OWhat
bond O)is
as Hyou
outthe
]orientation
a ion.
dativeO will
of
know
coordinate
the
H
[Co(NH
shown,
that
screen 3)6]copper
2+
These
bonds ligands
compounds
must form are[Fe(H
usually often
in
3 4O)(H 2]O)not
exist
certain
6
2+
2] in replaced
2+ [Co(NH copper 2+
complexes under
[Cu(NH )4(
to the solid bonds 2are above and H to stability the ion solid bonds areand above and
−
Figure +2
6.4 The [Cu(H
the +2
2+
H
ion is an ion in which Figure In this 25.7
Multidentate the section state. you ligands
will factors
learn Hto: might The increase formulathe of arelative
Ocomplex H tells of usthe number type of3/27/19
ligands, but there
you. Those HOOC–Haround
Figure C
469839_25_AQA_Chem_510-535.indd
covalent
225.14 the
or central
bond
paper Htheforming
formed
H
6
towards
H
Hbetween
ion. 514 CH
an octahedral
the
for you.
2 –COOH
Those ligand rules replacements HOOC–H
Figure C
225.14 reactions.
H
Hof a complex H CH 2 –COOH 2:11 PMligand replacements
molecules or anions This below is thestate
important plane
over H of
as the
+1 state rest.
coordinate copper? are bonds no definitive
a varietymust form below
relating in the the
certain plane
formula of the rest.
orientations ion to its structure,
−
−
• DescribeAFigure
ligand
range 6.4the
and
of The shapes
[Cu(H
the
complex central O)
shaped of
2 ions
]2+ complex
6 metal
ion.
can complexion.
be formed ionwith of central cations
shed
ohed bondmetal are ion Even Figure Ligands 25.8 that
attached H form an to
H amany dashed CH2coordinate bond
i.e. the are bonds
arrangement
istoto Figure
of a metal
ligands 25.8 C atom
aroundO
the H or
central H ion areCH2–COOH
metal ion. However:
6 ifIn the a coordination in number Hof a is complex 4 or 2, water H can only
HOOC–H ACcomplex HOOC–H
The 6-coordinated copper(II) E–COOH complexes are actually The 6-coordinated
distorted octahedral copper(II) complexes are actually disto
ions 2+
a central
4-Coordinated complex ions 4-Coordinated
iswe ion which Cuand,
around and
the 2
section range
central 2+ion
20.7,of surrounding
ion. found ligands.
that Ammonia
values an effective
could be used ligand predict for 2the
coordinate bebonds ]3+to the
ate of(dative
the screen covalent) or ever called
Figure
act
complexes
A range
• likelihood
Describe
as a behindofforms
multidentate
25.6
a number
example, the complex
of
monodentate
as ofthe redox the
molecules
effect the of
top
ions
complex plane
water orcan
and
reactions.
2+ ligands.
anions[Cr(NH
as
liganda of
formed
bottom 3
)the
6 •with
due screen
An
(Figure
complex a variety
ligands
O
to example
6.5).
the or
ions of central
are with
position of
further a cations
a multidentate
co-ordination
complexes of awaythe H number
loneas
than the pairs
the ligand
of
top six
of usually
and
others. isbottom
have ligands in
ligands are further away
25 TRANSITION
and
solvent are a N
range
bound
on the C
of
tocomplex Co
surrounding C
a central cation ion
ion byH2+
N must
ligands. − form
Ammonia in is an
octahedral positions effective H ligand and,
so that the for N C C
six electron pairs around the central ion are N
gands attached 2+paper. The 3+two [Cr(NH ligands attached These are different
lessto comm
4− O
− Ag+ These − are25.9 less common, and they can take up one ofsolution
two
EDTA . ensush
a example,
Which forms
of 2−the the M complex (aq)/M (aq) )36]3+ (Figure
Hsystems 6.5).
in O Figure will oxidise the 2− −
electrons.
These
EDTA So• Explain
evenCo
isClligands
usually
co-ordinate
though coordinate
are
how polydentate used
bonds. theoften
water, orientation
bonds
inligands not
alkaline to
ClH replaced O,NHO shown,
3the
hasbuffered
repelled
two when as
lone copper
solution
far apart
pairs EDTAThese
as tocomplexes
possible
of is
ensure
Clligands
usually
electrons, (Figure are
it undergo
is
25.12),used
the
both often in not
anion Cl replaced
alkaline buffered when copper comple
sa molecule
are above and
or anion HOOC–H C to
system: theCo 2+
H ion solid
forming H must bonds an formCH 2 are
octahedral–COOH above and
in • complex ions Hwith a Oco-ordination number HOOC–H C
H CH –COOH
−
2 H NH 2 2 H of H 2
ligand
form.
This is bindreplacements
All
important to the central
the acid as metal
COOHthe cation
reactions.
coordinate groups lose
bonds their hydrogen ligand
form. Allreplacements
ions thetoacid. acid
form COOH
the four reactions.
usually
anion groups have ligandslose their in hydrogen ions
ye stones,
central metal ion EDTA
occur on 2Bris – an
belowthe abbreviation
oxygen
the plane atom of for − so
the ethylenediaminetetraacetic
=it
rest. would V must be form
impossible Hin certain a for theseorientations
The two structure
3
of the rest. Co the
→ shaped
orientation complex+shown, Eion complexes, such Tetrahedral
x ion by co-ordinate
are formed Figure
Multidentate
EDTA
•
Fig 25.11Show
4− Cu25.8 by (aq)
Co-ordinate
. central
use of
ligands
Br
diagrams 2 (aq)
bonding inH hydrated how Fe 2e
cations
–1.09
tetrahedral Tetrahedral positions, Figure
H although
EDTA complex
4− Cu
2+
25.8 few
.structure
four co-ordinated Fe as comp
anedioate (calcium around of
lone the
EDTA pairs inis to forming
givenform ion.
transin an two octahedral
Figure coordinate 25.8. 3+bonds 2 to the Co , whereas the two
2–
N
3 2+
→ Figure [PtCl 6.4 ] [Cu(H
The have −O)afor ]square
2+
ion. planar (Figure 25.12),
514Cl 9.exist
Figureb 68 25.6
ligands Deduce Octahedral
4-Coordinated complex ions
Cl
cisE and values
shaped complex Cl complex
isomers
of M (aq)
ion Cl • complexes
M - [Fe(CN)
(aq)
4
The
+ e
[CuCl
6
]4]Cl , [CoCl
4-Coordinated complex ions
the3—
6co-ordination
systems
2− in
Cl 2−
]or and [FeCl
Cl −
]Cl complexes
Cl The are[CuCl tetrahedral 2−
4] , [CoC in
te on the inner Ligands lone
Other that
pairs
Figure 25.9.
Cl
polar form
ofH1,2-diaminoethane
molecules, Then many besides decide H3N coordinate
Clwhich
water, can ofalso
A range
theseare
The bonds
of
systems
co-ordinate
six
complex loneto
separatedwith aa
could
pairs
ions to canmetal
metal
are andbeshown
be
oxidised
ions.
formed atom
so Cl number
it
In
with can
4excess
by: a variety ion
of
actstwo are usually
of ascentral
have
a 4cations a linear
The six lone pairs are shown
H H
on The bond angle at th
H The bond angle at the central metal atom foror ion in diagram.
109.5°.
− 2+
2– coordinate +bonds to –the arrangement
− NH of ligands − (Figure 25.12). −
2EDTA is
nation Asnumber of a− EDTA
OOC–H
These is2are
Cusually used 2+
in alkalineCH 23+–COO buffered solution
2+ OOC–H
These to forensure
+
areCusually less it is anused
common, the inligand
anion alkaline
andCH 2–COO
they buffered
can take solution
up one to
of ensutwo
2Oless common, and they can take up aone of two different shapes.
3+3
ney. they grow called ammonia
So multidentate
even solution,
though Cu water, exists
ligands. as
H [Cu(NH An → )a2Cr
3example (H O) ]surrounding
+(aq)
of and Ag
multidentate exists as isligand is
2O, has two
Figure 25.6
bidentate ligand.Cr 7 (aq) + 14H (aq) 2− + Cr 6e and range
4on 2the oflone
(aq)2diagram. − 7H pairs O(l) ligands.
These of electrons,
which
form 2Ammonia both
effective and, the These form
2+Cl H H form Cl
a complexClion is the HOOC–H
[Ag(NH E ) = 2C
] +
(aq).
+1.33 CoV. ion must CHin 2example,
–COOH NH forms the bondscomplexwith [Cr(NH )6]3+ (Figure 6.5).
flow of urine out of EDTA form. occur on
Co[CuCl
4− All . 4Hthe
3 2 2− acid COOH
3N the
]N C oxygen atom
[FeCl groups Cr]3+so it would
− lose their coordinate 3
be hydrogen
impossible form. [CuCl All 4for
ions
the 3
the
]Nto
2− form acid
these COOH
the
two anion [FeClgroups ] − adding lose their
coordinate
The hydrogen
bonds
above
with ions
the
Themetal above complexes may ion.complexe
C be Cformed 4by concentrated Thishydro
o-ordinate bonds to it the CN –C
orientation N shown,4 N
gynding
stones,
extreme are
Fe pain. formed So even
Tetrahedral
EDTA In 4−though
addition . H3N tocomplex
to Npolarwater,
forming Cu Cmolecules,an
H C 2 O,
octahedral
has
anions
N
CH two 2 central
can Fe
lone
Cl– form
also pairs
■ Complex ions ion.
co-ordinate ofEDTA electrons,
This
Tetrahedral makes
4−bonds
2+ . to both complex
metal
3–
central
2–
metal makes
anedioate ligands.(calcium Cl– −Figurelone pairs 25.15 form two coordinate NH3
−CH EDTA2 bonds
acid toto[Cu(H
multidentate the CN
−Figure andCo
2O)
NH
, –2+
25.15 whereas
6Cl]these
3
, [Co(H the
2HO)6] CH
two 2+ and Cl [Fe(H − EDTA 2O)acid 3+
6] to. [Cu(H
multidentate and2O)6]
2
nes, are formed EDTA
occur on ions.isFor
OOC–H
514 H 2C
O an
the abbreviation
example, oxygen
2− H – when
shaped
NC atom
Hcomplex forso
anhydrous
2−
CH ethylenediaminetetraacetic
ion
H 2it–COO
N would
copper(
3–
II
− be impossible
■ Complex ions
) sulfate is added OOC–H for
to 2acid.
concentrated
C The
2–
2− two
H structure 2− 2–COO –− Cl C
The lone [CuCl pairs of
2+ , 1,2-diaminoethane
]acid, [CoCl 4H] CN and [FeCl are] 2+six separated
complexes The and
are [CuCl so it4can
tetrahedral ] ,Hof[CoCl acts inA Cl4]a and
as
shape. [FeCl 4] six complexes are tetra
te on the inner
Cl Cl HOOC–H 2 C Cl Cl 2 CH Cl hexadentate Cl Cl hexadentate
hydrochloric the solution becomes 2–COOH 3yellow-green due to the formation
Stereoisomerism in complex ions Stereoisome d-block metal consists
–
Cl Cl
–
4form H CN – NH The
−N 4Cl to NC
lone pairs are
− 2+, whereas
shown The
complex lone pairs 2− isare
ion shown
oate As
ney. (calcium
they grow
of−OOC–H
lone EDTA pairs 2C2–
isto2given H in ClFigure
two H coordinate 25.8.
CH2–COO H2bonds [CuCl the 2−Co
]ion isOOC–H yellow/green 2C CN 2+ the and twoH[FeCl Cl 4CH ]−Co 2is–COO Cl − on
orange. [CuCl ]ion yellow/g
Figure
The
Figure [CuCl 25.6
bidentate ligand.
bond 4] ions.
25.9 angle Fe at 3+
the central metal on atom the or
diagram. 4 The
Hin
These
Figure 3N Fe bond
109.5°.form
25.9 Ptangle at the central metal atomthe or
diagram.
4 in
These Au
109.5°
form
Figure 25.8 Co2+ A bonds d-block Cl– sometal complex asofaion Cl consists
ligands. NH3 These of coordinate
aared-blockmolecules metal orion nega su
ndration
the inner
flow energies
of urine of some out of loneIons
metal pairs NC
Co as
such
– of 1,2-diaminoethane
Cl
[Cu(H
NC 2+
Fe
NHNH 3 3 are
Co
CN separated
)4(H2O)2]2+
coordinate Some NC
and
complex with
]2– Co
it Cl
the
, in ions
can CN N can
acts show
C either N Auoptical Cl Some
or geometric Hbonds
complex
N with
(E-Z) Ag the ion
iso
N C 2O) C ]2−– , N [Cu(NH and [CuCl which a C
gAs they grow
extreme [FeCl pain.4] −
So even
bidentate ligand.
The above though
ion is complexes
Figure 6.5 The [CuCl
Hwater,
[Cr(NH ) 6
]
CNH
] 3+
H3 46 with
ion.
may O, has
be
Cl
3
NH3formed
– CH two [FeCl
2 molecules lone
central ] −
4by metal
Square oforligands.
pairs
adding Cl ion.of
planarThe 4
electrons,
This
concentrated These
above
makes complexes
complex areboth
asNH molecules
Clhydrochloric
–
ligands may Cl or
arebenegative
water
formed centralions
molecules,
by
Square metal that
adding 3
Cl
ion. Hhave
planar 2O, a
This
concentr amm
makes lon
com C
w of urine Hydration
Cu2+
out –1ofenergy occur on
HOOC–H
Six
−H3N
metal
Cl – 2C
lone Pt pairs associated
Cl are NC
shown Cl
2a
on CHnumber
Pt –COOH
2the CNof
diagram.
Cl −CH EDTA EDTA
multidentate
anions
Cl4−Six
–
−HCN can and
N
are
lone Crform
3+
known
Pt pairsClsix Clare
3
coordinateshown Cl on the
PtE-Z diagram.
+Cl EDTA EDTA
multidentate
4− canand form
nes, are formed
OOC–H
acidcomplex
EDTA Hto Othe
C
2 [Cu(H
Figure
The is Figure
word ions.
6.5 oxygen
usually
The
used
2HO)
The for25.15
[Cr(NH 6atom
2+
]3Hused
molecules
6the
) ]3+
, 3+[Co(H
ion.
ammonia insoCHCH 2itO)
–COO would
22N is6]‘ammine’
alkaline
and
ligands anions 2+ 2
and
buffered
bondedbewithSquare ligands
impossible
[Fe(H
Occasionally to two solution
the planar
Cl
letter O) are
OOC–H
acid
central3 3+ water
for
to complexes
6a] 4-coordinated
‘m’s in metalC
to.2 [Cu(H these
ensure molecules,
ion two
H O) can
it is6OH 2+
]Hthe Hshow
−
Cl H
N
, [Co(H
3
2O, 2ammonia
,anion
and CH –COO isomerism.
Cl
2cyanide
Ag
O)6] out −2+ NH
ions,
and3 molecules,
Square CN
[Fe(H
Occasionally
−
2.O)NH
planar 3+
6a]planar .3, c
com
4-coo
ascomplex turns toasbe square
nm /kJ mol H
reme pain. Cu2+
bonds are Cl–called
2with
the Cl the
Nligands.
name. C central
The
2+ [Cr(NH EachC 3)6coordinate] metal
Nion
ligand CN 2ion
iscontains
called a and H3hexadentate
atNleast
hexaammine so 2+ as one well
chromium(
atom −, Co
2
bonds
as with )2+ ion.a with
being lone described
Cl pair the2of central −metal ion andhexadentate
so well as being de
ioate (calcium
Cl– –499 lone pairs
form.
Figure The
DoNH to
All
25.7
not
2− word form
thecan
confuseused acid
–fortwo
CN with
this the COOH
ammoniaamine,NH groups
ligands
which CH His bonds
2
indicates N
Cllose
‘ammine’
2central – aThese
− –NH
to
with OH
their
Octahedral the
two
are
group. and
hydrogen
letter
III
octahedral
fewer ‘m’s ,cyanide
whereas
complexesin
in NHions
2− number ions,the
tocan form CN
two
thanshow theThe.
the anion ligands
tetrahedral
E-Z tetrahedral
NH3isomerism share These their
4-coordinated
− is Octahedral
with are lone
square
fewer
monodentate pairplana
comp
compl in wn
Figure
[CuCl
multidentate,
H
electrons.
O 25.9] is
3These yellow/green
it is
name. The [Cr(NH3)6] Hion alsobe
– described
donated
N and to 3 the [FeCl as ]
hexadentate. is
metal orange.
2 ion Figure
[CuCl
multidentate,
forming A 25.9
few
a ] 3is yellow/green
co-ordinate
NH
complexes it is
with also
a described and
Complexes [FeCl
as
with a ]
hexadentate. orange.
the is called a hexaammine
The
chromium(III) ion. 4
ligands share their lone pair with empty orbitals in the
Cl 3+
n the Cl inner
– –390 lone
HOOC–H 2 pairs
EDTA
bond.
4 C
The of
4−
2+.ligands 1,2-diaminoethaneare said octahedral
to
2 CH
be –COOH
co-ordinated are 2+ separated
4
to
Usually the
or have central and tetrahedral
a 4-coordinated so
metal it ioncan and
3
acts
Clcomplex
as a
bonds square formed
that ligands. planar between
has no overall
4
Usually the charge
or optical d-block
a 4-coordina meta
linear
is squar
isomeris
2optical
Anions such H as chloride H ions, Cl , can also behave as ligands and can Hisomerism
form with bidentate
−
2 2
H3N Co Do Pt
Complexes not confuse Cl this with amine,
with a co-ordination Complexes
HCo
which N indicates with a co-ordination
a –NH group. 3N co-ordination Pt number co-ordination number
As they grow –305 Even
bidentate ligand. ifform
complex theof
number ionscoordination
ofsuch
6 have as in [CuCl
an ]2−. number 2number ofof4 usually
atwo,complex bonds four orformed issix. 4 The or 2,
‘cis’between of water
42–have a can the
the only
d-block metal
of 2formhave a–
ion and the
469
ligands aret
Figure
Six
the number
the
Square
‘cis’
25.8
Anions
planar
ligands
sucharrangement
as chloride ions,
complex
the 4‘trans’
a complex
CN Cl−, can
form is usually
also behave
3–
whereas
as ligands and those
4− Cl
Square
Sixcan
the
form
lonewith
form
number
a
planar
pairs charge are They
tend
complex
shown toare
‘trans’
be
on ofthe sometimes
tetrahedral. called
diagram. EDTA canwith
whereas Also, coordinate
those
platinum
4− form
−lone pairs are shown on the diagram. EDTA iscan
w of urine out of2− –
ever octahedral
act as a monodentate of a
ligand tetrahedral
due arrangement
The to six
the lone pairs
position areform ofsquare-planar
shown the six lone coordinate pairs of linear arrangement
–281 Cl of
Co co-ordinate
The overall bonds
charge H offrom a[CuCl H
complex ligands
Co ion to the
is always central
the
− sum metal
of
They the ion
individual
arebeing
described
sometimes
as its
called Cl coordinate Cl bonds. aThe ligands ared bic
NH 3– 2– NH –
OOC–H complex C ions such as ] . CH –COO pair donors) (Chapter 18).
2−
Figure 6.6 The [CuCl ] ion. CN
ligands. of ligands. arrangement of ligands. ligands.
Z isomer 2 3 E4Cl isomer E-Z isomerism Z isomer NH
in 3
square E isomer E-Z isomerism
as planar complexes form square planar
2 on the diagram. These 3 form
reme pain. –18914 bonds–co-ordination
electrons.
Occasionally with
charges the
of central
thenumber.
a ions and molecules
4-coordinated metal CHfrom
ionion and
which
complex theso form as
complex
turns square
well is made. bonds
as planar
So,
Occasionally with complexes.
described the a central
4-coordinated The metal bond ion angle
and
complex inturns
so as square
well out asplanar
to beingbe squco
)6out to be square planar.
2
Cl The overall NC
charge ofchargea complex CNis always the sum ofCl
pair the ]3+individual Cl
is donors) (Chapter 18).
Fig 25.12 The structure of complex ions coordinate bonds with the
Figure in 25.7
this case, the net is 2- because CH Figure
the 6.5
complex The [Cr(NH
ion contains ion. a Cu
The likenumber
Au ofis dative
)2H 3N bonds Agin forme inH
2+
Figure 25.18 ofNthe Cfour Cl 2+ CFe N 2 Figure
iscentral
90°. 3
25.14 Co
Figure
multidentate, shows 25.18 it2ofthree
it complexes.
is examples
also described of
theoctahedral
as 90°. ions.
theNhexadentate.
Figure 6.6 The –1562 [CuCl4] ion.
multidentate, itthe isions also described as inhexadentate. + 3This 2occurs plan
2−
EDTA iscentralusually used in alkaline buffered This
solution occurs toSo, in
ensure planar complexes
] is the anion Pt(NH Cl as shown
25 TRANSITION METALS
Clions.
charges and molecules from which the complex made.

HWater is byfewer far most common ligand complex The strengths
Cu
Key term NC These2O CN are anion and in number H2N than
surrounding ClCl – − cations
the tetrahedral
(Figure 6.6). metal These
4-coordinated
ion. 2+ are
This
[Pt(NH makes fewer in number than tetrahedral 4-coordin
[Pt(NH )2Cl 2] the NC CN 3)2isCl‘ammine’
–1413 Fe
form. the− All
in this
co-ordinate 32+ case, bonds net charge
Cl between Cois 2- water because Aqueous
The the
molecules word
2+ complex used
−ofEDTA
complex
andion the
for
Figure 25.18. The
contains
different
multidentate Au
ions
ammonia anumber
Cumetalligands
and
There
Cl ions of are dative
can H
two as
withN bonds
the
two
3 different Ag
letter formed
coordination
‘m’s
ways
in H2+3in
by the
which number.ligands
Figure 25.18.
the ammoniawith
Common The th
The
Keyco-ordination
term
NC
numberFigure of Even
a Multidentate
Usually OOC–H25.7The ifthe
central Clthe
– a24-coordinated
469839_25_AQA_Chem_510-535.indd
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Canionacidcoordination
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Cisplatin
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Usually
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Figure
4isions
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called a 2,
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25.16
to
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ion that
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Do not confuse as
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The hydration
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O
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the which indicates number.
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group. Common
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The co-ordination number EDTA
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the
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ions
Also, pla
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Complexes 4 or Cl−2, water
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and tho
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is the number CN
of co- Figure
electrons.
those25.9 is used to form NHthe 3 co-ordinate bond. Anions
high such
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chloride on the
the
2
, can
central
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also cation draws
23
ligands
6
electrons and can in formO–H
the
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bonds
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from ligands.
ever formcalled
− ion act 9. square
69 Of
sharing
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the three
Octahedral
a lone
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pair complexes.
ions
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shown
electrons. nH2above,
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ligand O(l)complex The
due → An
the The tobond
first example
[M(H twolone
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six
ions
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such O)angle
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as
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of square
square
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the lone drawn planar
planar pairs ligand
are complexes.
complex
square
of isomersCo
is planar The
because bond The
they angletwo
are Cuin
non-linear
structures squar
ordinate bonds to the metal
OOC–H
ligands.isEDTA TIP
Figure 2number
C 25.14 of 6 H and the
shows
H last oneCH
three a co-ordination number
Cl– 2–COO examples
of − the water
Cisplatin
of
2
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H24.
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ItCisplatinare
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H+individual
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complex ions shown above, The the
complexed first
overall two water
charge have ofamolecules
aco-ordination
complex to
ion is this
always theproducing
sum
to ofkey ions.
electrons. The
Six25.7 hydration
lone pairs andare
[Pt(NH 3 2shown
) of some
Cl ] cations
on the are
diagram. listed
of2+
superimposable.
the charge
Table
complexes
4.EDTA H O
25.5.
of 4−
the
Use
may
can This
have
form
platinum(II)
table is
six the
distorted ionThe
coordinate isfeature
shapes.)
NH net
exactly So, charge cancelled 2+ superimposable.
stereoisomers.
onchargea bycomplex
H 2 of two
theO There
theion pla
neg Tis
TIP TIP
Figure 6.6 The [CuCl ] ion. coordinate of bonds with the
Figure
CN Remember
Multidentate
answer
number3–
question
469839_25_AQA_Chem_510-535.indd
N
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N 514
charges 2– number
Figure ions and
25.14 ]3+(aq)
2molecules
shows from which
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examplescomplex is2+ made.
of
(aq)octahedral
33/27/19 +2:11 PMions.
Cisplatin is such a 3+
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forms
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metal
O)
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ion.
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as such
complex
an
on
2O)
a 5OH]
2+
square
ion
anti-cancer
a complex contains a+
planarCuH
ion
2+3O (aq)
due to
complex the forms
different
ion which
and three-di
is are
used n
3– − Cl
bonds
EDTA
attached
If asked
Ligands Key is
to
H22–withOan
Figure the
abbreviation
to a wedge-shaped
draw
that
term
central
25.16
a displayed
form many
metal
for
coordinate bondion
central
This – NH and
anion chargesso
bonds
andwhy
3 multidentate
explains
as Clthe
four
well
supplied
to Ifaqueous
surrounding
as
asked
a 6metal
being
Cl by to acid.
the
Hcations
Clsolutions
− O described
draw
2atom The
chloride
(Figure
of most
charges
aordisplayed
ion
6.6).
as
structure
transitionare 3on
ions. metal
the ligands (if they are ionso
is the sum
charges of the
supplied charge by
Even if the coordination number of − EDTA
a complex arrangement is 4 and
or 2, of the
water atoms.
can only 2+ compoundsarrangement of2] 2+thb
NC Multidentate
OOC–H
drug.
ofmultidentate,
are EDTA C
CN
2coming
ligands
outit2ofis
iscisplatin,
given inthe
Cl alsoFigure screenCH
described –COO
25.8. as has,charges
hexadentate. [Fe(H drug.O)
on ] 3+
2+
the ligands 3(if
[Co(NH
they Ions are )
of
] 2+
ofions).
d-block The +net
metals
[Cu(NH3)4(H2O)
H2Ocharge
have a may
2+
stron
of a Cl
structure H 2 O of H OH H the 2 H N
3 The such asion
hexadentate
Cl − CuSONH 3Hin,2FeCl
O
fact, 3four
2
structure
, Co(NO H
separate N
33)2 lone and of CrCl
pairs NH
cisplatin,
3ofare moderately
electrons NH theand one
6
acidic.
called
Fe act as
ever
Themultidentate
co-ordination
a Femonodentate
number ligands.
Co due
ligand An example
toused The platinum,
4
of Au a multidentate
ofthe two chlorides H
ligand N andthe
3 is Ag
the two nitrogen H N
3 The platinum, atoms are thealltw
Co Hthe position the lone
Cuor +pairs of
3represent
CN Ligands or paper
coordinate that
metal form
ion is the many
towards
bonds between
number Cl
you. ofcoordinate
Those
co- the Nthose In oxidation isbonds
2The Figure
Oto statestoterms
form athe
Ions highermetal
25.14
coordinate
OH of
co-ordinate
cis
2than atom
d-block
and 3+, bond.
bonds
trans
the metals
The H
polarisingion
arrows
3Nbetween
are are
usedhave
relatively
power ofathe
NH
in 3strong
the
the small Nsame
central tendency
and way
metal H3highly
N as they
The tocharged.
terms form
NHare cis
3 in comp
and Th
org
NC electrons. Cisplatin
Figure
Co EDTA 2CN
H25.9
4−is
O ordinate . abonds
neutral
OH2to the metal complex, Au ion H3Nsharing [Pt(NH
Cl ofsamea3NH )
lone2 H Cl N ].
plane.
pair
3 2 ofIt Cisplatin
is Ag
electrons. neutral
H N H is3 N a
because neutral
NH the complex, [Pt(NH same
3 ) 2 Cl ].
plane.
2 It is neutra
Cl called
+
3– and attached
H multidentate
atoms to
2– in a dashed
the NH ligands.
Cl bond
ligand are
An ionexample is even greater.
– The
3
of FeCl
relatively
chemistry. a This
6-coordinated
causesCl
multidentate
and H
small
3 a release ligand
atoms and inof even more
copper(II) the
highly
3
NH
whichCo
is charged.H ions and the loss of
ligand
complexes favours They are
covalent
are highly
actually Cu
bond
chemistry. polarizing
formation
distorted oct
CN ligands 2+Cl charge Cl H22COof
TIPthe the H
platinum(II) H 3 CHion isNH exactly cancelled 2+ charge byHthe 2O of first the
two platinum(II)
negative 3 ion2is O)6exactly
6+
cancelled NH3 by t
TIP HOOC–H from surrounding ligands. 2–COOH
at the CN
Figure
EDTA must behind
EDTA 4−be 25.14
. shown. is the an shows
plane
abbreviation three
ofCltheexamples
Cl screen
for
Ofwater the
orof
Clethylenediaminetetraacetic
three
molecules
octahedral
3H O
2
complex resulting
7+ lastmust
ionsOH shown
ions. 2
in above,
oxyanions.
be shown.
the
acid. H3two
For
TheN have a co-ordination
example,
ofstructure
neither
NH3 [Cr(H ]H N
3
al displayed
wedge-shaped
2– Cl Six
bondMultidentate
Remember
122 lone pairs
charges
paper.
supplied
The
–
Ifisasked
that are
Ntwo the
ligands shownby tointhe
ligands
ligands draw on chloridethe diagram.
Na displayed
attached
Cl number
nor
ions. and2-coordinated complex ions
[Mn(H
molecules Trans
of and
2O)
EDTA which
6 complexes
H
the
6]O exist
2
4−
implies
favours
one in aas
can form
charges
H+ ions from
the
co-ordination
aqueous
‘opposite’
covalent
top
solution. and
number
six coordinate
supplied bond
byion–dipole
bottom
Instead,
–+ ]notice
4. the
the3 that
NH formation.
ligands
loss
chloride inthe
2-coordinated
ofbonds
two are Ions
water (Chapter
ions. Trans
ammonia
from
further H O
of molecules
2
groups
away4) with
implies ‘opp
than 1 liga
and
are a
th
CN 3– 520 Cl of EDTACl given 3+ C CFigure 25.8. eight each of these ions results the formation
tatin,
of the thescreen Cl octahedral
bonds
EDTA Co
ClHis with [Fe(H
an 2–
the O)
abbreviation
2
astructure
6 ] 2+
centralof tetrahedral
metalfor
cisplatin, Au ionand [Co(NH
and
CrO4 so
the – 2– 3 ) 6 520
] These
2+
2+
asMnO ion–dipole
Hsquare
well – ligands
Nrespectively.
ascommon beingplanar
Ag [Cu(NHbonds
H2acid.
are
Odescribed
3often
)
HThe
4 (Chapter
(H
3N that
2 O) 2+
not 2+
asversion,
structure
2 4)
replaced with
linear ligands.
when copper
theThe complexes
most common und
attached tosolid wedge-shaped bond The most 2-coordinated complex isligands one formed betwe ato2
and
al514
CN 2– Ligands
The
tetrahedral
to
HOOC–H
the 2O that
platinum, C– form
bonds the many two are
square Cl above
coordinate
chlorides planar CHCl
NH
2–COOH
3 bonds
and the +opposite
ligandtwo
[Fe(H to342O) a+nitrogen
metal
Theeach
replacements
] linear
2+
other
atom
platinum, atoms in
or are ion
the
reactions. allPolydentate
[Co(NHare
two in +3the chlorides
) ] 2+
and 2–soand
+.CrO3/27/19
are
2:11the opposite
the
PM two
[Cu(NH
chloride
3)4(H
each
nitrogen
+ 2O)2] 2+
ions. othe
srds
o you. Those
l between the N of are Au
EDTA
H OFigure
multidentate,
2coming
below Cl
isthe 225.14
out
OH it2ofisinthe
coordinate
given plane also
H HFigure
of N
3screen described
H
bonds
the H
rest. Ag
3 between
25.8. N H
as hexadentate. NH N
3 the ions, NPolydentate
Ag [Cr(H ,6 H
and N
2 3 6 ammonia,
O) ] 6+
(aq) → NH 3 2[Ag(NH ) ]+
2H O(l) + 8H 6
(aq) 4 (aq) ions, Ag , and ammo
CN called
Clsame multidentate
plane. H + ligands. Cl An Cl example 3
Cisof a multidentate
same plane. ligands ligand + is
3 2
ligandare Clor Cl Water, inammonia, chloride andmeans cyanide i
Figure 25.8 implies ‘on the same +side’ –+(aq) this instance Cis implies
that just ‘on the tha
dashed
he NH Cl3 bond paper
HCo
HOOC–H
The Fetowards
N4− 6-coordinatedAg 2C andNH Hyou. atoms ThoseH in Au
copper(II) theCHNH Co
2–COOHcomplexesligand Figure H25.14
are
[Mn(H N actually 2O) H36Ag ]7+(aq)
N Cu Ag →
distortedH NNH
2H 2O(l) octahedral
+ 8H + MnO –
4 (aq)
ne ofCN the screen or attached
ClEDTA H O
3 Cl
. OH
3
H N
3
NH 4-Coordinated complex ions
It +is Water,
ammonia a
3
linear H ammonia,
complex.
N
molecules NH
3
chloride
The
and
3
bond
the theyand anglecyanide
form is
only ions
180°. one usually
It
are dative is a
ammonia behave
linear
tobond with
eachmolecul as
complex mon
the
Au toClamust dashed be CHHbond
shown.
3N are Agbottom a H3N are Figure 25.19 thechloride ions next other.
2 2 3 3 3 3
o Figure complexes 25.19
2-coordinated complex ions The
NHas the
diagram top shows
and ligands2-coordinated complex ions further awayThe than diagram shows
others. a actually
HOOC–H
472 H22CO Cl C CH N 2–COOH Cl NH3 The 6-coordinated H2Ocopper(II) complexes are distorted octahe
draleligands
ligands attached Cl
tetrahedral
molecular
behind isthe model
plane of
ofare thecisplatin. square
screen planar
Atoms These they form
are molecular less only
linear common, one model dative and
of bond
able they
cisplatin. to with
form
can Atoms the
two
take central
or
up more
one d-block
dative
of two metal
bonds
different ion
w
Cl Figure 25.17 Cl orreplaced Figure 25.17
−
EDTA 520These
EDTA an is
Cl abbreviation
ligands
usually
2−
used often forin not ethylenediaminetetraacetic
alkaline buffered This
complexes when
It is issolution
the
better copper complex
asThe the
to touse acid.
complexes
top ensure used
and
the The E-Z itinstructure
bottom undergo
organic
issystem
the anion
ligands of chemistry
naming are further asThis
these Tollens’
It isis
away
is the
better
isomers. reagent
thancomplex
to
E the
use
(entg toot t
ge-shaped
nds are above bond and Cl The
are Cl
most
represented common as spheres 2-coordinated and are complex able is the
to [Cu(NH
areform one most formed
two
represented common
or more between
as 2-coordinated
dative
spheres silver
bonds
and arewith complex
the central the metal one form
ionan
edral square
paper.
of EDTA HOOC–H
planar
ligand
form.
[Fe(H The isO)Ntwo
All
C
given
2
2+ C
replacements
6] the acid
ligandsinHCFigure COOH attached
HN 25.8.
reactions.linear CH
groups
[Co(NH
2 –COOH
3)6]lose
2+ distinguish
These their ■ Figure
ligands hydrogen 13.15
between
are often
) ions
(H aldehydes
O) to
not ] 2+form resulting
replaced and
the anion complexes
ketones.
when copper It is can
distinguish
also
complexesbethe very complexstable
between
undergo
the
e ofscreen the rest. ions,
colour-coded: Ag4−Cu2 + ,bonds
andplatinum ammonia, (grey), [Ag(NH hydrogen +
3)2] . Tetrahedral
meaningcolour-coded: across)
ions, Ag
3 4 +is, and
2 equivalent
2
ammonia,
platinum to
(grey), trans
[Ag(NH and3Z)2](zusammen,
hydrogen + meaning across)
. known meaning is
dral +
to
HOOC–H
the Figure
tetrahedral
EDTA solidCnitrogen
25.8
. are■H Figure above
square CH
and
planar
Fe
13.15
2–COOH + ligand formed resulting
Common when
replacements complexes
linear
the
shapes complexwhite ofThe
reactions. can
precipitate be very
ligands stable
ofare silver and
often areformed
known
chloride dissolves as chelates
as chelating
when in
the age
dilu
wh
ou. Those (white),
Figure 225.14
H H3N (blue) Ag and NH chlorine is equivalent (white), to cis.
nitrogen E-Z
(blue) system
and 3/27/19
chlorineincludes 2:11 PM
many is equivalent
examples to
whic cis
edral
3
ed bond are BilalFigure
below
square isClthe
It planar
(green).
Hameed
HOOC–H
a25.8 linear plane
Which Cl complex.
Clof the
Hisomer 4-Coordinated complex ions
H is The
Common
rest. Cl linear
shown?
3
bond
shapes Cl
Clangle
of ammonia isbeThe ligands
180°.
complex
named [CuCl Itare
solution
(green). is4]2−
ions
using aoften ,linear
[CoCl
and
Which
cis
known
and the ]2−
complex.
4isomer
as
and
cream
trans.
chelating
bidentate
is[FeCl
Theprecipitate
shown? bond ]−agents.
4ligands, complexes
Transition
angle Ethanedioate
ofwhile is the
are
be180°.
ammonia
silver
Elements bromide
named
negative
tetrahedral
solution ions
using disso an
ionciai
The 2C
6-coordinated copper(II) CH2–COOH complexes are actually distorted octahedral
f the screen −Bilal
−
EDTA
Hameed
OOC–H
These is2are
Cusually lesstop H
used
common,
complex H 4-Coordinated complex ions
inions alkaline
andCH2–COO they −
buffered
can
The
on The
six
take
concentrated
lone
bidentate bond
solution
upasThis
pairs
one
are
ligands,
angle to
ammonia
shown
of ensure at the
two while
Marginalizer
differentit
solution. isthe
central the negative
hexadentate,metal
anion
shapes. atom ion derived
forming
or ion upinfrom
concentrated to six
109.5°. EDTAdative ammo (ethbo
Cl or Figure 25.17 the diagram. These form
2−
This
complexes is the N ascomplex the
C C and used N bottom in organic ligands chemistry are
Only further
hexadentate, the Z Tollens’
oraway is cis the
forming isomer complex
reagent
than the
up of to
to the used
others.six in organic
dative
complex bonds
shows chemistry
per any ion
Only asZTollens’
(Figure
the
anti-cancer or13.16)cis
act i
ands attached form.[CuCl All 4the 2− acid COOH
]N2− O inaldehydes
C Cnot [FeCl groups 4] −
−
andlose These their
coordinate
The areabove hydrogen
bonds
less with
common,
complexes ions
the to
and may form Othey bethe can
formedanion takeby up one
adding of concentrated
twoItdifferent sha
hyd
distinguish
These
EDTA is
Clligands
usually
4−
between
are used often Cl Nreplaced
alkaline buffered ketones.
when E
central copper
solution
or It
trans
metal isdistinguish
to
ion. also
complexes
form Thisthe
ensure is
makes complex
it
inactive between
undergo
is the anion
against aldehydes cancer. and It ketones.
is E
thought or trans is also
that form
cisplati theis
are above and Fe HOOC–H
formed Tetrahedral
EDTA
−Figure
2C
when . Hthecomplex
25.15
ligand replacements reactions. H
white precipitate
CH2–COOH
of− EDTA silveracid Figure
■multidentate
to [Cu(H
chloride formed 13.16 O)
dissolves
and when ]2+,Othe [Co(H
in dilute O O)precipitate
white
– –]2+ and [Fe(H of silver 3+.
O) ]chloride disso
ligand replacement is only partial – only four of
replaced. The overall reaction is:
Key terms The ion making the attachment via a lone pair of electrons is called a
ordinate and [CuCl4]2− is four co-ordinate 2– a2+complex
Cl – [Cu(H
ligand. The resulting
2O)6]
ion is called
The ion making the attachment
+ 4NH ion. [Cu(NH3)4a(H2
via a lone pair 3of electrons is called
is larger than H2O and fewer ligands can A ligand
Key 28is a molecule or anion
terms
23
An example
ligand. The of a complex
resulting ion ion
is with water
called a as a ligand
complex ion. is [Cu(H2O)6]2+ (Figure 6.4
that has at least one lone pair 2+
he central copper ion. 24 [Cu(H O)6] is pale blue whilst [Cu(NH2+3)4(H2O
The transition metals
Aofligand is a and
molecule
bondsortoanion
electrons a An example of2a complex ion with water as a ligand is [Cu(H2O)6] (Figure 6.4
– that
central has
2+
Cuelectrons
at least one lone
metal ion by a dative or pair deep blue. H H
Cl of and – bonds to a O
co-ordinate Cl bond. H H H
A central metalbondion by is aa dative
dative or The steps are similar to those above for Co2+. Th
tion of complexes with multidentate ligands.
23.1 The general properties of
co-ordinate H O
co-ordinate H
bondbond.
O H
more than one lone pair so they can form covalent formed between the
– A co-ordinate bond is a dative acts as a base removing protons from two of the
Clligand and the central metal ion.
transition metals
H
nate bond. Examples include ethylene diamine, covalent 9.70 Shapes
bond of complexes with coordination no. 4
formed between
A complex ion is an ion in which 2− H the Key in [Cu(H
terms 2 O)O ]
6 Cu
2+ to
2+ form O The Hion making(H
[Cu(OH) 2
the O)
2
attachment
4](s). Th
H The resulting ion is called a
ligand.
via
EDTA4−. These complexes are usually more ▲ Figure 3 number The shape
ligand and the of the or
central [CuCl
metal
4] ion A ligand
ion. is a pale blue orprecipitate O of copper hydroxide. W
▲ Figure 1AaPale blueof molecules
solution of anions O is a molecule anion
Cu2+ HAn example of a complex ion with w
With four ligands, VSEPR complex
are ion
to a iscentral
boundarguments an ioncation
in which
predict
by that
H thatthe hascomplex
at least one is
concentrated ammonia
lone pair O is added,
H the precipitate
monodentate ligands. This increased stability is 2+
[Cu(H2O)6 ]co-ordinate
, the pale
a number blue precipitate
ofbonds.
molecules or anions H of O electrons and bonds to a H
Learning objectives: tetrahedralTheand this
elements is
are usually
from
bound the
titanium
to a case;
central to copper
cation examples
by lie within are
deep thetheblue CoCl
d-block solution
4 and
elements. containing [Cu(NH 3)H4(H2O)
opy change of the reaction. Study tip
H
of [Cu(OH)2(H2O)4], and the deep blue H
central metal ion by a dative O or
O H
− ligands,
2
➔ Describe the characteristic [Zn(NH3)4]2+ ions.
co-ordinate bonds.
solution of [Cu(NH3 )4(H2O)2 ] 2+ ammonia
co-ordinate bond. has H replaced H H
both OH H and
O tw
en represented as en forproperties
short) isofathebidentate
elements Practise writing equations for A co-ordinate
Figure 6.4 The [Cu(Hbond O)is ]2+a ion.
O
dative H
ught of as two ammoniatitanium
ligands copper. by aHowever,
to linked short there are complexes with four ligands [Cu(OH)
that
covalentare bondsquare
2
(H
formed
2
6
O)
2 planar,4](s)
Hbetween H the+ 4NH (aq)
3 [Cu(NH
O
3)4(
the step-by-step replacement AFigure
ligand
range 6.4
and
of The [Cu(H
the
complex O)
central
2 ions
]2+
ion.
metal
can ion.
be formed with a variety of central cations
ch en can replace two
➔ water
Explain molecules:
these in terms of which showsofthat onefactors
ligand ScOH
otherCrthan
with
Ti Vanother. Mn FeThey
electron
2+
Co Ni Cu and
repulsion
A complex
Zn a range ion
must is anbe ion taken
of surrounding
6
in which
ligands. Ammonia is an effective ligand
2+
Cuand, fo
2 H
electronic structure. into account. A range offorms
complex ions or can be formed 3+with a variety of central cations
2+
(aq) + 3en ➝ [Cu(en)3]2+(aq) + 6H2O(l) are straightforward but can be and
a number
example,
area bound
range to
of molecules
the complex
of asurrounding
central cation
anions
[Cr(NH
ligands.
)
3 6
by Ammonia
] (Figure
O 6.5).
3 is4an effective
2 2 ligand and, fo The shape of the [Cu(NH ) (H O) ] ion
Specification reference: 3.2.5 HN Theforms [Cu(NH [Cr(NH]3)32+
O
tedious, 3and it is easy to make 3)4(H2O)NH 2 6 is octahedral, as expect
tities seven entities example, the complex ]3+
H (Figure 6.5).
The transition metalsmistakes

co-ordinate bonds.
with charges. Make H3N co-ordinate ion. The four ammonia molecules O e
molecules of ethylene diamine release six of Cu NH3 NH3
sure each step balances for both arrangement
▲ Figure 1 The d-block elements (shaded) and the transition metals around the metal ion withH the two H
23.1 The general properties of

ber of entities on the right in this reaction H3N Figure 6.4 The [Cu(H2O)6]2+ ion.
(outlined)
ligands and charge. above and below the plane (Figure 2).
ignificant entropy increase as the reaction goes NH3
Across a period, electrons are being added to a d-sub-shell (3d in Hthe 3N
transition metals
A range NH
of 3complex ions can be for
favours the reaction. Synoptic link case of titanium OH
to copper). The elements from The Cu—O
titanium to bonds
copper areare
Cr3+
longer (and
and a range thereforeligands.
of surrounding wea
2
Look back
bonds,
metals. They are good conductors of heat and electricity. as would
They are be
hard,expected
example,because
NHforms
3 water
the complex is a
[Cr(NH
igand EDTA4− can displace allatsix Topic 8.1, Theligands
water Periodic
Hint ▲ Figure
strong, and2shiny,
The shape of the
and have
H3N
ammonia.
high melting and boiling
Cr3+
points.The octahedron is slightly distorted.
Table, to revise the blocks of the
example:
objectives: [Cu(NH Cl–
2+ elements. H3N NH3
The
Periodicelements
Table. from titanium to copper lie within
These 3 )4 (H
physical the O) 2 ] ion.
d-block
2properties, The
together with fairly low chemical reactivity,
are Examples Replacement include iron (and itsby chloride ions – change in
analysis
make Ethylene
dotted linesmetals
these diamine
are notextremely (en)
bonds, Cl– they
isuseful.
also alloy NH3
+heEDTA characteristic
4−(aq) ➝ [CuEDTA]2−(aq) + 6H O(l)
called ethane-1,2-diamine and co-ordination number
analysis
2 steel) for vehicle bodies and to reinforce concrete, copper for water pipes,
stiesof the elements seven entities construction lines to show the square- H3N
and qualitative
9.71 Tetrahedral 1,2-diaminoethane. complexes Its formula NH3

o copper. and titanium for jet engine parts that must withstand
When highaqueous temperatures. copper ions react with concentra
planar arrangement of the NH3 ligands Figure 6.5 The [Cr(NH ) ] ion. 3+
2 Complex formation and the shape of 24

4− releases six water ligands. The
ReactionsScof Tiinorganic compounds is HinNCH 2CH
aqueous 2NHsolutions
2. Each Cu2+nitrogen Cl–
and qualitative
nese ofinEDTA terms of V Cr Mn Fe Co Ni Electronic

Cu Zn2 configurations in theFigure acid there
d-block elements is a changeNHin 3
both charge and co-ord 3 6
Cr3
structure. Hint
es on the right in this reaction means that there Figure 2 shows the electron Complexes with
atom a co-ordination
has a lone pair whichnumber makes of 4 generally
The word6.5 The form
used
Concentrated [Cr(NH
for a
the) ] ammonia
ion.
hydrochloric ligands is ‘ammine’
acid with two letter
provides 3 6
3+
a ‘m’s in
high
Cu2+arrangements for the elements in the first
Synoptic ion.link
H3N
complex ions
Cl the name. The [Cr(NH3)6] ion is called a hexaammine
– 3+
chromium(III) ion.
increase
eference: as the reaction
3.2.5 Electron goes shellsfrom left to
are often tetrahedral
right.
referred rowcomplex
itofa bidentate–
theCld-block. ligand. Thenot
Do Cl
word − ligands:
used for
confuse thisthe with ammonia
amine, which ligandsindicates
is ‘ammine’ a –NH withgroup.two letter ‘m’s in
elements
– 2
the name. The [Cr(NH ) ] ion is called a hexaammine chromium(III) ion.
[CuCl4to]of aschelates
‘levels’ or ‘energy levels’. Cl 3+
avours theand
o-ordinate formation 2− is (complexes
four co-ordinate In There
generalare there
Cl –
some are further
two outer examples
4s
2– electrons and
Anionsas you
such go
as across
chloride the
3 6
ions, period,
Cl , can also behave as ligands and can form
−
2+ + 4Cl − group. [CuCl4]2−
Cl – to the inner 3d sub-shell.complex Do not confuse this with [Cu(H amine, which
2O)6]
indicates a –NH
elements
2
ds)l− isover larger complexes
than H2Owith and monodentate
fewer ligands ligands.
can electrons are added
oftheligand substitution reactions – This explains ions such theasoverall
[CuCl4]2−.
▲ Figure 1 The d-block elements (shaded) and transition metals
similarity of these elements. The2+arrangements
Anions such as chloride ions, Cl , can also behave as ligands and can form
of chromium, Cr, complex
and
−
6 Transition
Cl
gthe central copper ion.
objectives: (outlined)
The formation of complexcopper, ofSynoptic
ions otherCu, metal
Figure
do not 6.6link
ions,
The
quite[CuClboth
fit] the Mpattern.
ion.
The
and The d-sub-shell
complexThe
overall
2−
pale
ions
charges of theisions
4
suchblue
charge of
as a[CuCl
full and
colour ]2−. ionof
10) 4in Cu
(3dmolecules
the [Cu(H
is always the sum of
from which the complex
the 2+
2O)6is] made. ion is rN
individual
So,
yellow [CuCl 2−
]
4 is 2- because the complex ion contains a Cuma
ion. (Although the solution
–
6 Transition
3+ Cl
tions Across a period, electrons are being added Mhalf– , summarised
toCl afull
d-sub-shell Cu 2+
inaccepting
(3d Topic
in the 24.3, The overall charge of a complex ion is always
Figure the
6.5 Thesum of
[Cr(NH the
) ] individual
ion. 3+
what the terms ligand, and (3d 5 ) in Cr and there is only oneinelectron this case,in thethe net4s charge
2+outer shell.
2+
All transition metal ions can form Entropy
co-ordinate is a
bonds measure by ] of the degree
3 6
link Figure 6.6 The [CuCl ion. 2−

– charges of the ions Cuand
2+ molecules from which the complex is made. So,
inate bond, and case of titanium to copper). The elements from
It isA believed
summary Key
titanium
that term
of to
aacid–base Cl
copper
half-full are
d-shelland makes theinatomscentral[Cu(H
4
anionmore O)
and
2 stable
four]
6 charge will
surrounding
in the remain.)Cl
Cl – −
cations Again,
(Figure the
6.6). actual rep
electron pairs from other ions or molecules. The bonds that are formed this case, the net is 2- because The theword
complex used for ion the containsammonia a Cu2+ lig
ation number ofThecomplexes with
mean. 2+metals.
multidentate
They are goodligands. conductors of heat ofanddisorder
electricity. (Topic They 17.4,are Whyhard, do in steps. inThe co-ordination number of and the ion
ionofis is
Chapter
same The Cl− anion

ion has, fact, four separate Cl−lonethe pairs ofTheelectrons )6]3+one
ination
Topic 8.1, Periodic are co-ordinate 2− (dative) bonds. An ionway
substitution asThe
Key
or molecule a co-ordination
full
term outer
withmain
reactions a ofnumber
lone shell
some ofmakes
pair a the noble
central gas atoms
and four stable.
surrounding cations name. (Figure 6.6).
[Cr(NH ca
version
h the
se moreblocksof [Cu(H
than one
of theand O) ]
2 6lone pairto
strong,[CuCl and ]
so41 they ,
shiny, one andof
can form
3d have 4s
high melting chemical
and boiling reactions
– metal
Cl ion is thetake
points. number place?)
of co-
Cl–
those is used
tetrahedral. to form the co-ordinate bond. The arrows represent
Do not confuse this with amine, wh
3
the
n what bidentate Sc of[Ar]electrons
3d 4s2 that forms a co-ordinatemetal bond with a transition metal is
Chapter
ions. The Cl ion has, in fact, four separate lone pairs of electrons and one of
−
s neutral.
e.dinate bond.Suggest two These
possible formulae thatdiamine,
ittogether Electronic The
configurations
co-ordination
ordinate bonds to thenumber metal−ionof
of thethose
a
ions
sharing of of d-block
a lone pair of electrons.
entate ligands are.Examples include
physical
[Ar] 3da2 ligand.
Ti called 4s2
ethylene
properties,
Some exampleswith so the
fairly
of ligands low
are
Figure
more H2Omolecules
chemical
metal
3 The
, surrounding
ion NH
shape
Cl−that
is reactivity,
3, number
the
of
ofare
, ligands.
the
CN .
co-
[CuCl ] 2− ion
is used to form the co-ordinate bond. Anions Thesuch arrows represent
as chloride ions,theCl−, ca
4−
d EDTA . These complexes make
V In
these
some are metals
4s2usually
3 cases, extremely
two, more
useful.
four, or six ligands
elements
Examples▲ from
include
bond [CuCl
released and
toordinate
the
a single
iron
4]bonds
are 2— (and
free toto
transition
its
themove alloy
metal ion 4
Of the three
sharing of a complex
lone pair ions
of shown above,
electrons.
number of 6 and the last one a– co-ordination number of 4.
the firstions
complex twosuch haveasa [CuCl co-ordinatio
4
]2−.
n how the size of the [Ar] 3d
steel) for vehicle bodies and to reinforce concrete, outcopper for water pipes, Cl
h
of monodentate
[Cu(H the2O) 2+ ligands. Cr metalThis increased
ion. The resulting stability species is is To 122
calledwork
around,a complex the the
from
the high
configuration
greater
surrounding
ion. The the entropy.
number of the ion ofOfan
ligands. theelement,
three complex first ions write shown above, The theoverall
first two charge haveofaaco-ordinatio
13.1
complex ion
First-f
6] ofand b predict the shape
for jetof
5 1*
affects shape [Ar]
and titanium
3d 4s
engine parts that must down withstand
the configuration temperatures.
of the ion element Figure
number
using the6.6of The6 [CuCl
Periodic and the ] ion. last one
Table, from a co-ordination charges numberof the ions of 4.and
4
2−
molecules
of co-ordinate bonds to ligands that surround the d-block metal is
tropy change
answer.of the reaction. Study tip
5 2
mplex
in your ion. Mn [Ar] 3d 4s 122 in this case, the net charge is 2- be
termComplex ions
its atomic number. 3– Key■ 2– –
Fe called
[Ar] 3dthe 4s2co-ordination number.
ligand charge as enElectronic configurations in the d-block elements
6
nten howrepresented CN Cl central anion and four surrounding
he step-by-step replacement for of
short) all
7 2the
is awater
bidentate ligands Practise 3–writing ■ Complex
equations for ions
2– – Cl Cl
23
Co •
Figure [Ar]Ions
3d
The 2transitionwith
4s
shows the co-ordination
metals
electron arrangements number six are usually
CN for the elements in the Cl octahedral, for
first 2– The Cl ion has, in fact, four separa
−
mines the charge on the A d-block
The co-ordination
V2+ metal
number of a
complexthose ionis consists of a d-block
ought
en.
ls are How ofmany
often as two
referred ammonia
entities are
Ni there
row ligands
3don
ofexample,
[Ar] the
8
4s2each
d-block.linked
[Co(NHsideby 3of
)6]3+ a .short Worked the
example:
step-by-step O NC Electron configuration
replacement Fe
CN metal ion
ofis the
Cl
Co
number Clof co- usedAuto form the co-ordinaH
ex ion. A d-block metal consists of a d-block metal ion surrounded
complex of ionligands. These are molecules or negative ions + tb
=
Each enlikely
can signreplace two • water 10 1*
molecules: NC CN Cl sharing of a lone pair of electrons.
dict
or ‘energy the
on reference: 3.2.5 of theIn
levels’. Cu
entropy
[Ar]
general
3d
Ionstherechange
4s
with are for each
co-ordination
two outer 4snumber Fefour
electrons Vanadium,
ofare
and one
as youusuallyV,gohas
ligand NC an atomic
tetrahedral,
with
across Oanother.
the period, Cofornumber
They CN of 23. Its electron
ordinate bonds
Auto the metal
Cl ion
H3N Ag H3N
Zn [Ar]example,
3d 10 2
4s [CoCl ]2−.
configuration is: of ligands.
Cl O These are molecules
fromligands
the or
are
surrounding
Cl negative
waterligands. ions
molecules, that
Of Cl
the Hhave
threeO, a lone
ammonia
complex Cl pair
ions shownof ea
mole
nediaminetetraacetate, electrons
2+ (aq) + 3en ➝ [Cu(en) O ]2+(aq) Oare added
–
+ 6H to the
4
O(l) inner NC 3d sub-shell.are CN
This explains the overall
straightforward but
2CN 2can be2Cl number −. ofNH
2
6 and the last one a co-
ligands are water
63s
molecules,
63d34s2
OH −H
Cl, andO, ammonia
cyanideCl ions, molecules,
CN , chloride ion
=
1s 2s 2p 3p
hydrochloric
ntities acid is
▲
added
•
seven
3
Figure
similarity
to
Some
—
C 2 of
—
—
an
ions
Electronic
aqueous
entities
with
2
arrangements
these elements.
solution 9.The
co-ordination 72 Tetrahedral
number
ofarrangements
CNThetedious,
four
of chromium,are
and N complexes
square Cr,Cl
it isV(3d
planar,
−easy
and
to
for
make
Ocyanide
examples
122 2
−. and has the
CO 3
2−.
OH , and ions, CN The ligands share their lone pair with empty o
—
the
copper, C example,
elements Cu, in
dothe [NiCN
first
not quite ]
d-series.
fit [Ar]
the pattern. The vanadium
d-sub-shell is ion
full 2+ has
10 ) lost
in Cu the two 4s 2 electrons
ic link
airs on four oxygen — 4
mistakes with
M octahedral tetrahedral square planar
ns, the following changerepresents
takes
O —halfplace:
and — O electron
the
– (3d ) inarrangement
full 5 Cr and there of is only one electronelectronconfiguration:
in thecharges.
4sTheouterligands Make share their
shell. bonds lone pair
formed CO with empty orbitals in the central d-
ydentate
molecules ligands are
of ethylene diamine 22p3release 2 6 six 3+ of octahedralCl 2– N tetrahedral O 2– square planarbetween the d-block metal ion and th
linear
eed to2−understand isNH
argon − 31s22sNH 63s3+
a 3p sure each step2–
balances
in1sthe 22s22p63s23p
for between
both 6 3
2– 3d the
It▲ believed that half-full d-shell makes Cl the atoms more stable
ely
Cl
mber
remove
] and
of
d-block
the
entities
and4 co-ordinate bonding, Hsame colour
on changes
the Figure
right Hfrom pink
3 Ethanedioate
in
N this to
reactionblue. CN 3– NCbonds formed
Cl CN They d-block are metal
sometimes –ion and called the ligands
coordinate are dative
bonds.cova The
=
3N way3 as a full outer main shell makes the noble gas atoms stable.
CN 3–
Cl
ligands 2– and charge.
They are
O sometimes – called Cl
pair coordinate
donors) Cl bonds.
(Chapter The
18). ligands are behaving as
nges2
significant
simple 3d
molecules entropy
in the oxidation state366
4s
and increase as
of the cobalt? NH NC
H the reaction goes
392CN
O
Cl donors) Cl (Chapter 18).
OC
Fe
CO
+
Electronic NH3configurations of
Cl the ions of d-block
pair
=
ed in Topic 3.5,
ss2 favours H3N
Thereaction.
the
H3Co N Co 3 Cl FeCo Co
Cl O Cl
Ni
Co The Au number Ni of dative H 3 N bonds Ag formed H 3 Nby the lig O
of the twoand
amolecules
solution ions
of concerned.
aions. NC
elements
O CN
NC CN
Cl
The Au number Cl of dativeH N
OC
bonds Ag formed H by
N
+
the ligands with the d-block m
Fe Co as the coordination number. Common coordina
OC
3 3 CO
2
xsligand
water ligands EDTAin Cl NC CN Cl Cl
forthe
4− can displace NH3 water ligands
sible reasons theNCcolour NH3 all six
change. CNconfiguration of CN Hint
Clan element, asCl Clwrite
the Common
s1*
To work out the
O NH
the ion
Cl
▲ClFigure
of 4 A metal(II)–EDTA first coordination
complex
Cl number. Complexes withcoordination
a coordination numbersnumberare of 42 and will
or2 example: downCN NH 3
the configuration of the Cl
3
element using the Periodic Table, fromwith a coordination CO
Complexes number of 2 will be linear, CO those with 4a
s]2−(aq) + 6H O(l)
Ethylene 2– diamine (en)4is (occasionally square planar) and those with 6 are
2 2+ its atomic
[Co(NH )6] 3+
3[Co(NH
H
number. 3)6]
3+
[CoCl4] 2–
octahedral [CoCl 4] [Ni(CN)
tetrahedral ] 2–also square planar 2+ linear
Hs2 H
) +This EDTA 4− (aq) ➝ [CuEDTA] 2− (aq) + 6H2O(l) [CoCl4] (occasionally
2— square
393 planar) complexes and [Ni(CO) those may with 6 are
4] have distortedTrigonal octahedral shapes.) (Figure 13.15
tetrahedral called ethane-1,2-diamine square planar and
Tetrahedral bipyramidal
en.s2O
increase in Figure 4 Benzene-1,2-diol
▲octahedral (a)linear
ntities H Aqua seven ions entities complexes
2+ may have distorted The shapes.)
Nickel tetracarbonyl
net charge on a complex
(b) Iron pentacarbonyl
ion is the sum o
ase
s2
in entropy which Worked CN example: Electron configuration
3– 2–
Cl 1,2-diaminoethane. of V Its formula – Figure 6.8 Complexes of transition metals and carbon monoxide.
helate complexes
O H 4− 3– with If you dissolve the2–salt of a transition metal in water, – for example, Cl The copper net Cl charge on a charges complexon ionthe is ligands
the sum(ifofthey the chargeare ions). on The the d-blo net
on
4s 1*
CNEDTA releases six
Cu ofmonodentate water
–Vanadium, Cl ligands.V, has ancharged The
atomic number of is23.H2Its NCH 2CHcharges
electron 2NH2by . Each nitrogen
with NC sulfate, H the positively
CN H Cl metal – ion becomes
Cl
O Co atom has a lone pairAu
surrounded on
water the ligands (if they Ions are of ions).
d-block The +net charge
metals have a maystrong be positive,
tendency n
which makes + HCH3NHC Ag H3N
2 Oconfiguration
4s Fe acting is: O O
Monodentate and bidentate CO
—
CO
ities onOthe H right in this reaction means that (Figurethere
—
molecules H asHligands 1). Normally there are six water

2Cl
—
—
2
Ions of d-block metals have a strong C Ctendency to form complex ions be
2
CN NC molecules relatively small and highly charged. They are high
Co in CN C — C
C — C 22s 63s23p63d34s2
py ctronic Fearrangements
increase as the of reaction 1s 2p Au Such it Cla bidentate Hligand.
N Ag ions.
aqua H3N Most ligands, H O, NH , Cl , OH and CN , − − −
Hgoes from left to right.

an octahedral arrangement. species are 3called
—
H
Cl
– – 2 3
Cl Cl and O O
—
H N
=
NH
relatively small highly charged. They are highly bondpolarizing metal ion.due Theseto a hia
—
—
H O
—
which favours covalent with the central

formation. Ionsligands from
2
2+Nhas lost Cl
2
3– O H — C2– – CO
theO first d-series.
eH favours CN CN [Ar] The vanadium
CN
the formation of chelates (complexesClCl
O ClN —Cl Cion V — the
O
Htwo 4s 2 electrons and has the which literally means ‘one tooth’. Some liga
—
Cl
—
—
—
Cl
—
H
electron arrangement 2–
of Cl
Multidentate H ligands
– –— chelation which favours covalent bond ion–dipole formation. bonds Ions (Chapter from groups
4) with 1 ligands.
and 2COaresame less
=
electron
C — C configuration: C C one co-ordinate bond with the centr
=
OC
nds) CN Cl
over complexes with monodentate H ligands. forms two forms two
C CN
—
1,2-diaminoethane and the ethanedioate io

Cl Cl
—
63s 23p 6 +co-ordinate4)

—
2p ion–dipole bonds (Chapter with ligands.

—
1s 22s22pO 63s23p63d3
Copper(II) ion surrounded3– O Some
octahedralmolecules or2– ions, called multidentate
tetrahedral
Au – ligands, H3N have
square moreplanar
Ag than H3N FigureOC6.9 BidentateFeligands.
bonds
linear co-ordinate bonds
ble for carrying
CNFe oxygen H CoCl
– CO Cr
bonds with the same central cation and ar
H
Polydentate ligands
Ag Synoptic
Cl + link
–
olecules
octahedral 2+ ion 2– one atom with a lone
tetrahedral pair ofsquare Cl
electrons planar Cl Hcan
which bond to a transition
linear toothed’, Figure 6.9).
C nsists ofCoCl CN
an FeTransition Elements
Figure Au5 EDTA Cl– H3N 3N Bilal Hameed
▲ Polydentate ligands
Ni OC
C Cl CN metal ion. Cl Cl OC CO
stions
ation sites are taken
CNFe Cl up ClCl
Cl Co
Cl Marginalizer Au
Cl Entropy is a H3N ofAg
measure
+ Water, ammonia, chloridethey
the degree H3N CO
+ Water, ammonia,
andform
OC
cyanide
Bilal chlorideHameed and cyanide ions usually
The bidentate ligand 1,2-diaminoethane (
context to ‘en’) uses the nitrogen atoms
adentate ligand. This
C Cl Co CN
Bidentate
Au
ligands include: onlyions oneusuallydative which behave
bond have awith as pair
lone monodentate
theof central
electrons, to bili
d-b
ndsCloctahedral
are neutral and Study
• tip Cl H3N
Cl
Ag of disorder
Cl
H3N (Topic 17.4, Why do two points. In the complex ion shown in
nversion Cl O) ] to [CuCl
ofcharge.
[Cu(H 2+
Ethane-1,2-diamine,
Cl
tetrahedral 2−
sometimes
square called
planar 1,2-diaminoethane they form COor
only
linear one dative bond
able to with
form the
two central
or more d-block
dative metal
bonds ion.
with A numbe
the cent
OCN 4]sites , one of (Figure 2). Each nitrogen CO 1,2-diaminoethane attach to the nickel io
ve a negative
2 2 6 Cl ethylene
Both ligand Cl
diamine
of bidentate chemicalhas reactions
a lone pair takewhich place?) CO
number is 6 and the shape of the comple
is
he transition metals
mistry of complex ions

3+ H
occupy tetrahedral positions although there2+ are a few complexes with 2+
bondsiswith
EDTA
attachedan athe central Shapes
to abbreviation metal
wedge-shaped ion
of and so as ions
complex well as beingacid.
for ethylenediaminetetraacetic
bond described as
The structure H O H2O
four-fold co-ordination, such NH H planar,
are square O bond angle 90° .
Ligands that form many coordinate bonds to a metal atom or ion are as [Pt(NH
3 3)2Cl 2], that have a square2planar
[Fe(H2O)on6]H NH3 with[Co(NH the3)6] 2+
O 2+ number of ligands around
3.1 The general Tip properties

multidentate,
ofFigure
it isinalso described
25.8. as hexadentate.
of EDTA is given The15.15)
shape
H N of a complex NH3ion depends the
called multidentate ligands. An example of a multidentate ligand is areH2coming
O
Cu2+
out 2of the
OHstructure H screen3
(Figure
● in complexes central metal ion (thenumber
with a co-ordination co-ordination
of two, number
N shape is linear
● 2 – 3the
of the
the ligands
bond angle
central metal ion).
usually
180°.
or paper Fe Co Cu
4− towardsformyou.
a linearThose
H
structure with the centralFigure
metal ion 25.14
The structures
(Figure 15.15). are illustrated in Figure 6.7.
Pansition metals EDTA H O .
attached
OH
to a dashed
29
H N
25 bond are
NH O
H N NH
The shapes of complex ions2 cannot beO
H
2
In complex
3
ions with co-ordination
3
number:
3 3
NH The 6-coordinated
H Ocopper(II) complexes are a
TwoH common H tetrahedral complexes are [CuCl4]2− and [CoCl4]2−. The
H O HOOC–H22C Hpredicted by the electron pair repulsion
● 6CH –COOH
member that the ligands behind the plane of the screen or
theory that applies to molecules H relatively large size of –thethe shape ions,
2chloride is3 octahedral
compared and
EDTA is an abbreviation for ethylenediaminetetraacetic
the bond
to oxygen angles
atoms are all 90°
in2 water
acid.and Thebottom structure
O and molecules, means●that it is not possible forNHmore
3 than four ligands to fit round complexes as the top ligands are f
ached to a wedge-shapedthebond more simple ions. H
paper.[Fe(H The
H Ntwo theCligands
centralCmetalattached
N
4 – the shape is sometimes tetrahedral, bond angle 109° 5’ but there are
2O) 6]number
2+ of EDTA is given in Figure 25.8.
ion.
also a [Co(NH
number 3of)6complex
] 2+ ions with a[Cu(NH 3)4(H2number
co-ordination O)2] 2+ of 4 that These ligands are often not replaced when cop
eves:
coming out ofThe the screenfrom titanium
elements
● in
Figurecomplexes
15.13 with
Dative a co-ordination
to
covalent
to thecopper
bonding
solid in lie
an withinare
aqueous
bonds Cu of
2+ four,
the above
ion. Eachthe
d-blockligands
water
are usually
elements.
molecule
and
square uses a
planar, bond angle 90° . Cl– Cu+
em_510-535.indd 514 occupy
lone pair of tetrahedralHOOC–H
electrons to positions
form a dativeCcovalent
although there
bond arecentral
with the a fewmetal CH
ion.2–COOH
complexes with The transition
3/27/19 2:11m ligand replacements reactions.
paper
cteristic towards you. Thosefour-fold co-ordination, Figure
below such
2
the25.14
as plane
[Pt(NH
H
) of
Cl ],
H
the
that rest.
have a square planar Complexes with
9.73 Tetrahedral complexes examples – the shape is linear
● 2 – with bond angle 180°.
NH3 3 2 2
H3N Cl
ached
ements to a dashed bond are structure (FigureFigure 15.15)
HOOC–H 25.8
2C
H H CH2–COOH
co-ordination nu
Tip
● in complexes with a co-ordination number of two, the ligands usually
The 6-coordinated copper(II) complexes
The structures are illustrated in Figure 6.7. NH3 of 2 are usually li are actually distorted
4-Coordinated complex octahedral ions
hind
Tip the plane of the screen or NH3

Chemistry of complex An important
ions
multidentate ligand is the ion ethylenediaminetetraacetate,
2+
form a linear
In aqueous structure
solution, withii)the
the copper( ion central
N metal C byion
is surrounded complexes
C(Figure
six water
N 15.15).to form the
molecules as the top4−and bottom ligands are further away than the others.
Cr3+
Pt
O
–
O
per.
ms ofThe
he shapes two ions
of complex ligands
cannot be attached complex ion [Cu(H O) ] . In solid hydratedcalled
TwoSccommon Ti V tetrahedralCrEDTA These
Mn Fe complexes Co2
ligands
6
2+
Ni Cuare
copper(
Zn 2−[CuCl
are
EDTA
) sulfate
often 2− (CuSO (Figure
ii
and not
.5H O),Cl5).
[CoClreplaced
however,−
]2−. The 4 2
–
These
when are lessto
copper common,
complexes and
undergo they can C —take up
—
—
redicted by the electron pair repulsion there are only fourHwater N is
Cl usually NH used 4] copper( in N alkaline
)Cl ion. The4 fifth buffered solution ensure it is the anion
—
molecules co-ordinated with each H
e.
the solidappliesbonds areand abovewater and
relatively large size HOOC–H C
of the chloride
3
molecule in the solid copper(2 ) sulfate is associated

ions, ThisHcanNH
compared act
to
H oxygen
3
as a hexadentate CH –COOH
atoms
with a sulfate ion,2SO A
3
in
ii
water ligand using
few complexes with NH
lone pairs on four– oxygen 3
C —
heory that to molecules
molecules, means that Shapes
ligand
form. it is notAll of
possible thecomplex
replacements for
and acid
more
ii
both COOH
than ions reactions.
four
nitrogen ligands groups
3
to fit round
atoms.
. co-ordination
a lose
Complex
4
2−
their ions
NH
numberhydrogen
with
3
polydentate ions to
Cl
ligands form are the anion
O
—
— O Cl–
ow morethe
3.2.5 simpleplane of the rest.
he ions. –
the central metal ion. Figure Cr Cu 25.8 3+
Fethe Cl of 4 are planar
–
Tetrahedral Cl– complex Cu+ Cl–
metals
The shape 4− of a complex ion depends on number of ligands around the
Other polar molecules, EDTAmetal. ion (the co-ordination number3+ of the central metal ion).
besides water, called can chelates.
form dative Chelates
covalent can
bonds be used to effectively remove d-block ▲ Figure 3 Ethaned
HN
with metal ions. central
3
3+
[Cr(NH3)6] , CuIn complex
For4-Coordinated
2+
example, in excess
Cl
ions form H N
NH
Cl [Cu(NH
Clmetal ammonia ions Complexes Clcomplex
solution,
from
2+
Crwithions
solution.
Cl number
+
a form
Cl ions The [CuCl 4 ] 2−Complexes with a2−
, [CoCl
co-ordination 4 ]
number and [FeCl −
4] comple
Pt + 2
3)4(H 2O)2co-ordination
] and Ag ions form
3 3
ions withClco-ordination number: of The six lone pairs are shown – H
H6The transition metals
23 centralClshapes.
–
Hchelate The bond angle at the metal
▲NH Figure 1 The[Ag(NH d-block3)2elements
]−+. In addition− (shaded)
EDTAOOC–H
These to is are
polar and
Cusually the
lessThe
molecules, transition
used
common,
anions metals
inNH
can effect
alkaline
also and CH 2–COO
associatethey with−
buffered
can NH
take solution
up one
to
of ensure
two + it is the
different anionatom or io
properties of
3
2 are usually octahedral
Cl
2− on the diagram. 3
These form
(outlined) Clcations using dative 6 – the bonds.
● covalent shape For is octahedral
If example,
you when and
Cr + add a hexadentate 3
the
anhydrous bond angles
NH 3
copper(ii)
ligand
are all
such
90° 3
as EDTA to a solution Co
of a Cl –
2
A few complexes O with
Across a period,
Complexes with a
sulfate
co-ordination is added
electrons number to form.
of
are
concentrated
4 –
being
[CuCl
the
Allshape
added4the
]N 2− acidPtCOOH
hydrochloric
is
acid,
Ca d-sub-shell
transition
sometimes
to Cmetal theN
tetrahedral, [FeCl groups
Cr − contains
solution
2+
salt,
(3d
]the EDTA
4bond
in the Cllose
angle
3+
will
109°
their
coordinate
The –
replace
5’ but
hydrogen
above
bonds with ions
there all six
are complexes
water
the to form the anion
ligands may in be
the formed by
a co-ordination numbe
addin
s
●
yellow
6 are usually[CuCl 2−
4]H N
octahedral ions. NH 4− central metal Cl ion.CuThis makes –
Cl + –
of 4 are planar
portant Cumultidentate
HN caseligand isFe
of titanium the ion copper). Tetrahedral
EDTA
to ethylenediaminetetraacetate, alsoClaelements
−Figure
The number
3
. ofaqua
25.15
–
from
3
complex
complex iontitanium
2+O
ions
[Cu(H
NH
with
2toO O)–a co-ordination
2+
6]2− as shown:
copper are−Cl–EDTA number of 4 that
acid to
multidentate –[Cu(H and aO) – ]
2+, [Co(H O) ]2+ andO [Fe(H
4− 3
EDTA (Figure 5).metals. They are good Ions such as [Cu(H OOC–H
O)
are ]2+, [Cu(NH
square C planar,
2A few complexes ) (H
bond O) ]
angle
3 4 ClH2with2 H NH and90°
–
C —
[CuCl. CH ]
4 2
3 –COO
in which Complexes
Cl with 2 Cl 6 2 6
ion isconductors
2 6
of heat 2−,ofelectricity.
]and 2− They are hard,hexadentate −Tip
—
The [CuCl [CoCl
[Cu(H2O)
4C]or— and
2+ (aq)
6]anions +[FeCl
3
EDTA
4] six
4−(aq)
complexes
➝ co-ordination number
[CuEDTA] are tetrahedral
2−(aq) + 6H O(l)
in shape. − H
—
l PeriodicCl
The Cl a metal ClNH associated with a aco-ordination
number molecules are called The
Stereoisomerism
lone of pairs are shown
in complex io
3 2
4 2 are usually linear
—
number
Cl Cl H H [CuCl 2−
]ion Complexes with a Cl–NH
as is yellow/green and [FeCl 4] 4is Benzene oran
n act as a hexadentate ligand using lone pairs − 2 –
on anionsthe
four shape is linear with bond angle 180°. −
cks of the strong, 3+and shiny,complex and ions, have ●
andOOC–H high
the
Cl melting
2ofCoxygen
4and and boiling
molecules
are planar
– Complexes
attached points.
to theCH
with a –COO
central metal
Cl When –
anions act ligands, the overall +
th nitrogen atoms.
Cr
Complex ion are
ions with called Complexes
polydentate
ligands.
The
The
Figure withbond
Each
structures
25.9
a ligandare
ligands are
angle
In this
must have
illustrated
at the
equation, —
co-ordination
in
4 are
—
OatFigure
usually
centralOtwo 2
number
least tetrahedral
one
–
6.7.
of metal
species
lone pair of
on
are atom the
replaced or
diagram. 4
charge on the complex
by seven. in
These 109.5°.
co-ordination
ionusually
form
This increase
number
Pt
does nottetrahedral
of in ▲ Figure 2 3
itanium to copper lie

These within
physical the d-block
properties, elements.
together Cl
with fairly low chemical NH
reactivity, ion. coordinate Clbonds
4 are
with the
HN3
chelates.
[CuCl4] 2− Chelates
●in complexes can withbeNHused
electrons which
to] −effectively
a co-ordination
[FeCl
co-ordination
number it uses
removeofto
number
form
four, d-block
the
of thecovalent
a dative
N
ions.ligands
C
NH
number
usually▲ Cbond of with
Figure
particles
N 3 the
3 causes
metal
Ethanedioate
equalSome
a significant the oxidation complex
– increase
number ofin ions can
theentropy which show either optical
make these Figure
metals 15.15
extremely
The
6ofareshapes
The
usually useful.
of
above
complex
octahedral Examples complexes include may
iron 6.7 (and be formed
itsright.
alloy central by metal
adding ion.chelate This makes
concentrated complexeshydrochloric
ons from solution. occupy tetrahedral The3
positions4 number although ligands
there
Six
in
are aacomplex
few drives
ion
complexes the reaction
is typically
with
Figure
two, 3
four to
The
or the
shapes
six. + For
of complex
Squarethis
ions.
central metal
2
reason
ion. planar
4−few complex with
NH
],lone pairs Clare shown on the diagram. ClEDTA can 3+form six coordinate
Co – A complexes with 3
steel) for vehicle NHbodies haveand H to32N reinforce Pt aconcrete,
polydentate 2+Cl
copper ligands for Ptwater
are Cl pipes,
favoured EDTA over multidentate
Square complexes and
with monodentate
an3−)acid aplanar complexes can show E-Z isom
−2+ – H
gure 25.15four-fold co-ordination, such
Chemists as [Pt(NH Cl
OOC–H
2alternative that2have
to Cname
[Cu(H square
for planar
O)
dative
H ]
covalent
H , [Co(Hbonds HCHwhich 2–COOO) ]
they and [Fe(H
Occasionally O) ]
co-ordination
a . number
4-coordinated complex O
turns Ho
3
—
helate effect ligands.2 6 This is called 2
the 6
chelate hexadentate
Key
effect.terms 2 6
structure and titanium
(Figure 15.15) for jet engine bonds
parts that with must the central
withstand highmetal ion
temperatures. and so as well as being described as
—
often prefer when describing complex ions. The alternative name is ‘co-

Chemistry
mplexes
-ordination
with a
number of in complexes ofwith complex
a co-ordination ionsnumber
Cr
of
alsotwo, Cl
theCl
3+
ligands Types – of
usually‘co-ordination ligand O – compound’ Anof are planar complex
4octahedral is said to show six-fold
C—C co-ordina
]These are anafewer whichin number than the Htetrahedra
ordinate bond’, which gives rise to the terms
—
add a hexadentate ●
ligand such as EDTA to a solution
Figure
[CuCl
multidentate, 25.9NH
of 2− a
]co-ordination
is yellow/green
itd-block
isligands
also
Cl
described
Cu NH
Cl–
and Cl3 [FeCl Cu ++ –
Cl
as ofhexadentate. −–
Octahedral
is orange. in complexes can show O E-Z isomer
=
–
octahedral 315.15). isand tetrahedral complexes show four-fold co-ordination.
—
re usually
—
tion and the shape of
NH structure with the central metal Most Cluse only one
V Cr Mn salt,
Fe Cothe NiElectronic
form a linear 3
Cu Znwill replace andconfigurations
‘co-ordination ion (Figure
number’. Ain
4 the compound elements
is one thatlone pair
contains 4electrons
A complex toionform co-ordinate
ion a bond H N —C—
ion metal EDTA all six water ligands in the O
with the Complexes
central metal a ion. These ligandsUsually
or areof described
optical a 4-coordinated
orasanions
monodentate
isomerism complex
with bidentate that has it is no
ligands. also o
—
annot be number molecules are
H N Pt Cl Haemoglobin with Complexes
—
a complex ion, and the co-ordination number of a complex ion is the
with a Most complexes are formed by ions. However, p
9.chloride
74theShapes Square planar complexes
–
Two common tetrahedral Key
complexesterms
– are [CuCl
of
2−
3 4] and [CoCl4] . The
complex ions
2− Complexes with a Cl
=
on [Cu(H2O)6] as 2+ shown: C — C
repulsion Figure H2 Nshows Cl electron arrangements
the for the
because elements
co-ordination
they have number
only
Ometal in
‘one the tooth’first to hold boundonto the central
to a central
a metal cation
cation by(dens
cois
relatively large size of the number of
ions,co-ordinate
compared to‘cis’
bonds oxygen fromform the
atoms ligands
in waterto ofthe 2the central
are ‘trans’
usuallyco-ordination
linear form
co-ordination
ion. number number of complex using the uncharged metal atom. For example H
3
whereas bonds. those with a3,six
acharge tend O–to be tetrahe
—
4− can
—
n referred
es
Cu(Hand 2+ (aq) +
2O)6]molecules,
rowEDTA
means ofthat
the
4−
it d-block.
(aq) ➝
not
Complexes
The for
[CuEDTA]
Monodentate
is Co-ordination
possible shape
co-ordination
with
ligands Six
2−
more Square
aof alone
(aq)
compounds
NH number than
form complex
of+one 6H
four
contain
planar
pairs
O(l)
Cl
2ligands
dative
NH toare
Latin for
ion depends
complexes
3 Cl , OH
fit
− round
complex
shown
Haemoglobin
– on
which
tooth).
− andmay
the isnumber
CN −
4on
Examples
the
be are the
ofusually
red
Hcations,
.the
2of are
pigmentdiagram.
ofligands
monodentate
usually
tetrahedral
anions
linear
inaround
ordinate
blood. ItEDTA
the ligands
is responsible include
chromium H
for form
O, form
2all NH
carrying oxygen coordinate
complex with carbon monoxide.
H Th
levels’. the centralInmetal Some complexes
central metal with
ion Z (thea
isomer co-ordination
3
co-ordination from number
the number
lungs E
of
to the cellsof
isomer 4
centrala form
of metal
the body. a square
form
ion).
A E-Z
ligand
The is a
moleculeisomerism
square are
molecule planar
illustrated
or
consistsanion bound
of anin inFe square
complexes.
Figure2+ 6.8.
ion planar
The bond compl angl
equation, two species are replaced generalion. there covalent
orCr are
+
centralby
4
neutral (co-ordinate)
are
two usually
molecules
3
seven. outer
Figure bonds bond
tetrahedral
6.7
This 4s
(Figure
ion in aOccasionally
The with
with
a
electrons
15.14).
shapes
increase inSome the
and
of Examples
complex central
as you go
of co-ordination
awith4-coordinated
ions.
▲ Figure
ligands
metal
across
have more
ion
the
compounds
complex
4 Benzene-1,2-diol
than
and
period,
one lone to
sopair
as
turns
the
well
central oution
metal
as being
toin can
abecomplex
described
square as
planar. ▲ Figure 5 EDTA
gure 15.15 Cl The shapes of electrons
complex ions. are planar
addedcomplex
include: metal
Into complex
the inner ion.
complex.
Figure
ions3dwith 25.18
co-ordination
sub-shell. This aexplains
co-ordination
number: thetheoverallnumber of six. Four is ofofco-ordinate
90°. theelectrons
co-ordination that form
sites co-
are taken up
multidentate, it is also described as hexadentate. This occurs bonding.in planar complexes like the Pt(N
mber of particles causes a significant increase in

These entropy are which
fewer ion by
ain number than the 3− tetrahedral 4-coordinated ligand. Thiscomplexes.
HN ordinate bonds with same metal ion. Bidentate (‘two-toothed’) ligands,
elements (shaded) and 3 the transition Kmetals
Bidentate ligands form two [Pt(NH
dative 3)2Cl–2 ]forby ring system called a porphyrin whichwith actsmetal as a tetradentate
the reaction to the similarity
right. For of this
these 3[Fe(CN)
elements.
reason
● ● 6 6] the
NH–chelate containing
The
shape isthe
arrangements
complexes negatively
octahedral Cl with
charged
andof chromium,
example,
the complex
bond form two
angles ion Cr, [Fe(CN)
dative
areand 6]
–covalent
all 90° bonds ions inofcomplexes.
NH
n
3Nof ligands
3
complex
Pt
m_510-535.indd Cl ionsCu,over
514copper,
covalent
Fe(NO3)3.6H2OUsually
docentral
not ●
quite
Cl
(co-ordinate)
fitinwith
the
bonds
pattern.
with
3
containinga the
–
a
The4-coordinated
complex
positively
Bidentate
d-sub-shell 23.2 –isligands
called
charged An
Complex
isbond
full
octahedral
Hcomplex
‘haem’.
complex
include
(3d 10
Cl
formation complex
inion that
) 1,2-diaminoethane,
Cu
The
andisFigure 25.18.
ionhas
said
Cisplatin the to
co-ordination
noshape
H
show number
2overall
is is
NCH
six-fold
of
the such
2CH
complex There
co-ordination;
a metal
charge
2NH of a
ions
2 ,square
the are two
square
is square
planar different
planar Study
planar,
complex 3/27/19tipion
ways 2:11in
ntate are favoured Types complexes aFigure monodentate 25.16 H
2of
O)46ligand and tetrahedral in ashowcomplex number co-
109° complexes
metal –four-fold co-ordination.
[Fe(H ● ]ion
–3+the complex.
shape is sometimes NH
tetrahedral,
ethanedioate O ion, C2Oangle
3 2−
4 , and amino
5’CH butacids there(Figureare 15.16).
rons are being added to a d-sub-shell (3d in the andCH NH chlorideAlso,
O
CH ions could arrange themselves
toligand sites oa
—
—
s.alThis
ionsiscan called theand half full
chelate (3d
effect. 5 ) inby Cr and whereas
there isofonly thoseoneions with
electron aa in charge
the 4s outer tend shell.to+offormed
3
be tetrahedral.
ordinate
drug. bonds to 2 the metal ion O from platinum
possible to tends
Both
—
—
2
form co-ordinate bonds
Ni(CO) 4also a number
accepting
containing Pta neutral complex
complex with
between co-ordination
nickel atoms and number
Hcarbon 4 that
2+
aMost HPt 3
Most ligands use only one lone pair of electrons to form C complexes
co-ordinate bond are —by C ions. However, it is also form
● 2
opper). The NHComplexes C— the C surrounding ligands.
3 elements It with
is from
a
believed titanium
that a to copper
half-full are
d-shell makes the atoms more stable in the ligands usually bo
—
monoxide are molecules.

square planar, bond angle 90° .
m other
termsions or molecules.
number ofThe with the
Cl bonds that arecentral metalform ion.
formed square
These ligands planar are describedcomplexes.a as
complex monodentate usingThe the bond
uncharged angle metal in
atom. a squaredrawn
For example, planarare
nickel, complex
iron and
—
=
–
—
—
O
—
co-ordination OCl – H H
Key
d conductors of heat
same andway electricity.
as a full They
outer are
main hard,
shell makes to theholdnoble gas Hatoms Nstable.
—(densC— isC —a Ncomplex The two structures
Shapes of complex ionsisomers
metal becau
forming a ri
3)2Cl2].
because they have only ‘one tooth’ onto the central cation
NH chromium all form Cisplatin with is
carbon a neutral
monoxide. complex,
The three complexes[Pt(NH
H
6 are usually octahedral O HC CH O
(dative) bonds. An ion or molecule with aExamples
lone
shapepair Study 180°.tip
—
—
2 – the is linear with bond angle

—
NH
ddHaemoglobin
3
is 90°.
—
●
—
4s NH Latin points.A few

for complexes
tooth). with of monodentate + 3
ligands 2 include H O, NH , NH
have high melting and boiling
=
Co are illustrated in Figure 6.8.

superimposable.
C — C
This is the key feature with
=
Monodentate
[Pt(NH
orms )2ligands
Cl2] form one bond
a 3co-ordinate
3
dative with−a transition a co-ordination number
metal is Cl – C — C
A few complexes 2 3with N
15.6 Formation of 3complex
As you ions have
429
seen the [Co(NH )they
]3+ canion, act
withas brsi
number 2+ charge of the CH3 platinum(II) ion3 is 6 exactly can
H H
Electronic It configurations TIP metals− of the ions of
are illustrated in Figure 6.7. d-block
Cl 432 , OH − andplanarCN . −
—
of 4The structures
—
—
—
3+
Cl – are CH
a co-ordination O
rovalent
m_510-535.indd
rties,
moglobin (co-ordinate)
is the redbond
together 514
with with
pigment a in blood.
fairly low chemical
is 15
responsible Transition
reactivity, for−,carrying oxygen PtCl (NH O–
) 3 two metal
3/27/19 ions.
2:11
ome examples of ligands are H O , NH , Cl CisplatinCN . isdraw such The chlorine atom is in Period forms
3
H whichoctahedral
is are non-superimposable
shape. An octahedron has due to
six point
a adisplayed
square planar complex Nionsupplied and used as, has an anti-cancer
2 3 2 H
–
of 4 are planar
gure 25.16 Some Fecharges metal ion,by the chloride ions.
2 ligands have more than one lone pair of electrons that can form co-
elements
entral metal ion in a complex. 3
– If asked toion
2+ Nshell 2+
the lungs
xtremely to the cells
useful. of the body.
Examples The
include molecule
iron consists
(and its of
alloy an Fe and Figureso has 5 an
EDTA extra Co3+ a charge of +3 and as the
o, four,NH or six ligands
Bidentate ligands form two dative bond ordinate
to a single bonds with
transition
Cl the
drug. same metal ion. Bidentate ▲ (‘two-toothed’) ligands, arrangement of the atoms.
with a a complex ion. Thestructure of up cisplatin, the
a co-ordination
ies and to reinforce
3
number of six. NH
concrete, Four ofthethe
copper co-ordination
forform water sites
pipes, ofare taken 23.2 compared Complex inwith formation
the nitrogenand atomthe shape theofcomplexcomplex2ion ions has an overall charge of +3.
is To work outfor configuration
example, two dative the
covalent ion of anwith
bonds element,metal ions
CH 2first write
complexes.
platinum,CHtheCHtwo
3
The chlorides and the two n
469983_15_Chem_Y1-2_418-449.indd 429 13/04/19 10:03 PM
sulting speciesbonds
ovalent (co-ordinate) called number
Complexes with a Cl– H 2NCH2CH2NH2 , the
ring
ngine system
parts called
that a porphyrin
must which
withstand acts
Bidentate as a tetradentate
ligands
high temperatures. include ligand. This
1,2-diaminoethane, in Period 2. N
entral metal ion in a down
complex.
nds to ligands that surroundethanedioate the configuration of
469983_15_Chem_Y1-2_418-449.indd 432
the d-block metal coordinate
the 2−ion
element is bonds
using
is a neutralStudy
the between
Periodic the
Table,
tip [Pt(NH N from
The terms The [CoCl
cis and ]2− ion, with four ligands, is tetrahe
4 trans are used Synoptic
because the in the
13/04/19 10:03 PM
link
same
2Cisplatin Clcomplex, 3)2Clplane. 2]. ItCois 2+,neutral
plex is called ‘haem’. its atomicCrnumber. 3+ ion, C O 4 , and amino acids (Figure 15.16).– CH
2 Cu
+ HC Cl –
same CH
has a charge of +2 and each of 123 the four l
ination number. CH
figurations in the d-block Cl
elements and
2+O 2ClchargeH atoms
4 are usually tetrahedral
–
Cu of the
in the NH
platinum(II) ligand withion is exactly chemistry. cancelled
3 of −1, soby thethe two ion negative
– + –
P
NH 3 Figure 6.7 The shapes 3 CH
of complex ions.2
CH
must be shown.
Cl
Both Nligand sites of bidentate
Complexes
– COOH a
N – Shapes of complex ions
complex has an Look back atcharg
overall Topic
23 a displayed to the2-coordinated complex ions
rdination
tals
lectron arrangementsnumber H Nsix are for usually
the elements octahedral, in the for
first Study co-ordination tip number chemical reaction
sked to
3+ draw
3
Worked example: Electron charges Complexes
supplied
with a
configuration byligands ofthe
of 2Vare
2+chloride
usually
C bondions. same CCH3
Trans impliesThe reason havefor
‘opposite’ thisthe difference
notice3in
–[Co(NH ]shape
3+ ion,iswith
thethat amsit
6that
NH – usuallyNlinear CH
3)6] . As you seen )revise
Cl co-ordination number 2
HC 520 NH
CH of 2 are usually linear metalcomplex forming a ring. However, larger ligand than the ammonia molecule entropy. and
ucture of cisplatin, the The most common 2-coordinated complex is at
3
Complexes with a+ An octahedral complex
of 23.is Its The
saidelectron chlorine
to protein
show six-fold atomco-ordination;
is inCH Period 3 square planar octahedral shape. An octahedron has six point
theopposite eachion, other inare that allversion, andasso
–
Vanadium, of V, 2COOH
rdination 4snumber four are usually gohas an atomic number
Cltetrahedral, for
432
canmolecule
3
wo 15 Transition
outer metals
electrons andCr
co-ordination N you
as
number across the andTheperiod, platinum,
tetrahedral complexes theshow two
and
they chlorides
four-fold
so has
act asNi
co-ordination.
an extra 2+and
bridges
shell
between two nitrogen
around
metal theatoms
Cocentral
3+, has metal
a charge in of
ion. the +3 and the
ordinate
Cl
o ]
the
2−.
4 Hinner CH bonds between the N
N 33d
4 are configuration
usually tetrahedral
sub-shell. This explains the overall is: CH3
two Figureions.
▲ metal 6 Haemoglobinions, Ag , Aand
+ ammonia, [Ag(NH +
)2]number . of +3.fou
3
same 6–plane. +compared with the it isnitrogen atom
Cis form thefew
toimplies ‘on complexes
complex
the ion has
same an overall3 charge
of co-ordination
side’ – in this instan
9.75 Square planar complexes
1s 22s2complexes
Most 2p 3s 23pare 63dformed
34s2 by ions. However, also possible
dments.
mplex
H atoms
ions.
hangements
co-ordination in the
Theofarrangements numberNNH3of Fe ligand
four
2+ are NH
chromium,N square Cr,planar,and H3N using for
Cl Agthe uncharged NH3 inmetal Cl –
geometry as (Figure gas7).
3
N ] 2−. a complex 2Below the plane PeriodC of 2.this ring

atom. For example,
is a fifth nitrogen nickel,
C
It is airon
atom
linearand acting
Thecomplex.[CoCl ]2− ion,
4faulty The heaters.
with bond four Because
ligands,
angle it binds more
is tetrahe
is 180°.
ust be shown.
-series. [Ar] The vanadium ion V 2+ has 10) in
Figure lost the 25.19 two 4s electrons and has the ammonia molecules and the chloride ions ar
Cr
ite4 fit
rangement
and
the
there
2
of
pattern.
m_Y1-2_418-449.indd 432
CH
Typesis only of
The
electron
oneligand
d-sub-shell
N configuration:
electron
is
in the 4s outer
full
are
(3d
2
chromium
CH
shell. 25.17
illustrated
molecular inmodel
Cu
CH all
Figure 6.8. of
2-coordinated complex ions
form The
cisplatin.
a complex
a ligand.NThis atom is part2+of a complex
Atoms
diagram– with carbon shows
NH3 protein calledSomeCo , has a
monoxide.
globin. airon
complexes charge The three
thanareoxygen,
of +2 and
linear, N complexes 2+
it isone
–
13/04/19 10:03 PM
possible
each to suffocat
of the
example four
being l
Complexes
3+ CH2 with a 2– Figure 2– The sixth▲ Synoptic
site
Figure– can 7 accept
A
Pt
link
square an oxygen
planar molecule
This
complex as
is –a ligand.
the ofcomplex
−1, so the plentiful
complex
used oxygen.
in ion has an overall
organic chemistry charg
6
alf-full d-shell HC
Cl ofuse
makes Cl
theonlyatoms 2– more CH
pairstable 1s
The
inare 2
the 2s 2 2p 3s
most
6
torepresented
23p 6 3
3dCl– bond
common Theas
N
2-coordinated
spheres areas :Ocomplex Ita very
is is
better
N
the to use
one formed the E-Z betweensystem
[H3Nsilver➝ofAgnaming➝ NH3]+ t
ate co-ordination Cand
Mostnumber
ligands one lone of electrons form a co-ordinate Fe2+ to O2 bond is weak,
NC CNas monodentate 2 is not C good ligand,
The reasonAnaemiaforaldehydes
thisisdifference in shape isbethat t
ter 6main withoctahedral
are usually
shell makes
the central the NH3 ion. These
noble
metal gas atoms stable.
ligands are described
ions, Co2Ag
+ , and ammonia, Look back at
[Ag(NH Topic 17.4, ) Why+distinguish
3 ]easily
. meaning
do between
across) isthan a
equivalent condition and
to transketones.
which may and ZIt
caus
because they have only ‘one tooth’ to hold colour-coded: – platinum
allowing (grey),
thecomplexes
oxygen hydrogen
molecule to be given up tolarger
cells.
COOH + NH A solution
ligand containing the this
ammoniacomplex ion
molecule is calle
and
onto the central cation
Cl Synoptic
(densA isfew
chemical reactions link
with 3 2
number 2+take place?,
shortage of haemoglobin. The body suffer
figurations
H33N
ne dative Ag Cl Latin NHof
for
Cl
Co
+
3 theCo
N tooth).CH
ions
Examples
2 of
CHof3 d-block
monodentate Ni(white), nitrogen
ligands include H2O,(blue)
BetterNH , and chlorine
a 3co-ordination
ligands
revise than oxygen
entropy.
is toequivalent
formed
Ni can bond irreversibly
whenisthe
to used
around theto
in white
cis.
theorganic The
central
lack of
precipitate
E-Z
chemistry
metal
oxygen and system
ion.
the
of includes
tosymptoms silveralde
distinguish ch
include
ith a
complex −
protein molecule
−
Cl , OH and CN Cl
− .
CH2COOH
Cl It is a linear
(green). Which isomer complex. of 4 are
You
iron and soisdestroy
The
planar
will learn
shown? bondmore angle
about is
ammonia180°.
be named
haemoglobin’s oxygen-carrying solution
Aldehydes
A using
few andand
reduce
cis the
the
breathlessness,
complexes cream
[Ag
trans. (NH
and a pale
of co-ordination 3precipitate
) ] + to Ag (met
2 skin
number colour.fouo
Th
. Some ligands have more than NC
–
Clone lone pair of electrons form co-using Tollens’ reagent to test
CN that can capacity. ketones 123 do(Figure
not. The silver forms a mirror on th
gure 25.17 This
This C explains the poisonous concentrated
C effect of carbon
geometryammonia be loss solution.
of blood
7). or deficiency of iron in the
with ais the complex
figuration ▲ Figure 6 Haemoglobin
of the
ordinate ionClof
bonds withanthe element,
same metalfirst ion. write
Bidentate (‘two-toothed’) ligands,forused aldehydes in organic
and ketones chemistry
in as
tube,Tollens’
giving reagent
the name to
of the test – the silver m
ative
iona of thefor
Cl
example, using
element form two thedative covalent
Periodic
Complexes
bonds with
Table, from metal ions
Cl– monoxide,
of in complexes.
–
N which is a better ligand thanOnly oxygen.the
N – Carbon Z or cismay isomer
be treatedof bythe
Some complexes are linear, one example being
takingcomplex
‘iron’ tablets show
wh
with co-ordination number
distinguish between
monoxideO Topic 26.2,formed
aldehydes Reactions and of the
ketones. It is also the complex
iron(II) sulfate.
w. the plane of this ring isligands
Bidentate a fifth nitrogen
include atom acting as
1,2-diaminoethane, faulty
2–H2NCH
tetrahedral gas CHheaters.
NH the is
, Because often
it binds more by incomplete
strongly to thecombustion in
E or trans form is inactive against cancer. It+ai
Complex ions may have a positive charge or
[CoCl4] 2– [CoCl 2– 4 are usually
[Ni(CN) 4] 15.16).
2 2 2 Figure 7 group
▲carbonyl A square planar complex
ethanedioate aion, C24O] 42− , and amino
calledacids (Figure in aldehydes and
and.Figure
This atom is part of of complex protein globin. formed iron than when oxygen, the it iswhite
possibleprecipitate
to suffocate in aof roomsilver
with chloride dissolves in dilute
chloride ligands replaced
[H3N ➝ Ag ➝ NH3]
after entering
,2-diol 6.7 The shapes complex ions.
sixth site can accept an oxygen molecule as a ligand. plentiful oxygen.
ketones. Representing the shapes of complexthe ionc
Fele: Electron
2+ to O bond is weak, configuration
as :O is not a very of V 2+
good ligand,
ammonia solution
O and the
Synoptic link cream precipitate of Asilver
low intracellular solution
Representing bromide
containing
chloride dissolves
this complex
concentration
three-dimensional in ion
shapes is
on calle
whi
pap
salt of a2 transition metal 2in water, for example, Anaemia is a condition which may be caused by a is used in in organic chemistry to distinguish alde
given up to cells.concentrated ammonia willsolution.
An octahedral coppercomplex is said to show six-fold co-ordination; square planar diagrams this topic have thin red constructi
wing the oxygen moleculeofto23. be easily
elyancharged
atomic number
H metal
Its electron
– ion becomes surrounded by watershortage
and tetrahedral complexes
C ofshow
haemoglobin. Youco-ordination.
four-foldMThe
learnsuffers
body more aboutfrom M
a the chloride Aldehydes ionsreduce
visualise the
with
shapes.
water.
the [Ag (NH
These are3not )2]+ bonds.
to Ag (met Ano
ls O using Tollens’ reagent to test ketones do not. The silver forms a mirror on th
—
er ligands than oxygen

sHligands (Figure 1). Normally therecan bond irreversibly
are to the
six complexes
water lack of oxygen and the symptoms include fatigue,
—
Most O
469839_25_AQA_Chem_510-535.indd are O
formed by 520
ions. However, it is also possible to form shape is to use wedge bonds and dotted bonds
C—
22s
1sdestroy22pC 6haemoglobin’s
3s23p63dSuch 34s2 for
palealdehydes andTheketones in The aquated tube, complex
thegiving
paper the andname
is ablethetotest
dottedofbonds
form
go –inthe
links
silver 8) b
m
and so
tahedral arrangement. oxygen-carrying
species are called aqua
a complex H3breathlessness,
using ions.
the uncharged
N and aatom.
Clmetal skin colour.
For example, causes
nickel, ironmayand of (Figure
—
octahedral tetrahedral
—
H O Topic 26.2, Reactions of the

Ccity.
V— 2+NThis
has explains
lost the H
O
the
two poisonous
4s effect
2 electrons of
andcarbon
chromium
has the all be
form loss
a of
complex
Pt blood withor deficiency
carbon of
monoxide. iron in the
The diet.
three The tumour
latter
complexes Complex ions may have a positive charge or ar
cell. This halts the process of DNA
—
Isomerism in transition metal complexe

—
oxide, which is a better Bilal

ligand Hameed
than oxygen. are illustrated inmay
Carbon Figurebe treated
6.8. by taking carbonyl
‘iron’ group in
tablets aldehydes
which contain and Transition Elements
gands – chelation and effectively stops the growth of the tumo
=
tion:
H
C — C H3N Cl
13/04/19 10:03 PM
oxide is1s
often
2s formed O3s by Bilal
3pincomplete Hameed
combustion in moreiron(II) sulfate. ketones. Marginalizer
Representing
You have met the
isomerismshapes in of complex
organic chemistry. ion
—
2 2 6 2
2pmultidentate 6 3d 3
or ions, called
H
ligands, have than OH M M
its platinum content and there areshapes
sidewith effec
with the
Representing samethree-dimensional
molecular formula but on diff
pap
–
one pair of electrons which can bond to a transition

em_510-535.indd 520 Figure 25.20 Clinical use of cisplatin square-planar linear damage of
and their
diagrams atoms
hair in thisin
loss. space.
topic Transition
have thin red metal comp
constructi
3/27/19 2:1
geometrical
visualise theisomers shapes. (cis-trans,
These areor not E-Z isomers)
bonds. Ano
(a)1 (i) State what is meant by the terms:
(a) What
(a) What is meant
is meant by the byterm
the term transition
transition element?
element?
complex, .............................................................................................................................
....................................................................................................................................................
....................................................................................................................................................
.............................................................................................................................................
30
..............................................................................................................................................
26
.............................................................................................................................................. [1] [1]
ligand. .................................................................................................................................
(b)aqueous
(b) In In aqueous solution,
iron caniron form
can formcomplexcomplexions ions
which which
containcontain ligands.
.............................................................................................................................................
solution, ligands.
2(i)
(ii) (i)
TwoName
Name ofthe the
thetype type
complexesof bonding
formed
of bonding that
that by occurs
copper
occurs between
are
between[Cu(H a ligand
2O)6] and
a ligand 2+ and
anda a transition
CuCl 4 .
2–
transition element.
element.
Draw three-dimensional diagrams of their structures in the boxes and name their shapes.
9. 76 Skill check
.......................................................................................................................................
....................................................................................................................................... [1] [1]
[Cu(H2O)6]2+ CuCl 42–
3
(ii) (ii) Which
Which offollowing
of the the following species
species canas
can act acta as a ligand?
ligand?
Complete
Complete the table
the table by placing
by placing a ticka (tick) in
( the
) inappropriate
the appropriate column
column to indicate
to indicate whether
whether the the
species
species canas
can act acta as a ligand
ligand or not.
or not.
can act
can act cannot
cannot act act
species
species
as a as a ligand
ligand as a as a ligand
ligand
–
NO3–NO3
BF3 BF3
H2NCH
H2NCH CH NH2
2CH22NH22
6
26
+
NH4+NH4
shape: .............................................. shape: ..............................................
14 (d) The cyanate ion, NCO–, can act as a monodentate ligand.
(iii) Platinum forms square-planar complexes, in which all four ligands lie in the same plane as [2] [2]
4(i) State
the Ptwhat atom. is meant by the terms
There are two isomeric complexes with the formula Pt(NH3)2Cl 2.
monodentate,
Suggestions, theions,......................................................................................................................
structures of the two isomers, and, by comparison with
(c) Manganese
(c) Manganese Mn 2+Mn2+(aq),
(aq), show show
some some
similarsimilar chemical
chemical properties
properties ofa copper(
to those
to those similar IItype
of copper( IIof
) ions,
) ions,
isomerism
2+
Cu (aq).(aq).
2+Cu in organic chemistry, suggest the type of isomerism shown here.
.............................................................................................................................................
Use UseStructures
this informationof isomers:
this information and and the Data
the Data BookletBooklet to suggest
to suggest the formula
the formula of the of manganese
the manganese species species
ligand. in
formed .................................................................................................................................
formed in eacheach of the offollowing
the following reactions.
reactions. StateState the type
the type of reaction
of reaction taking taking
placeplace
in eachin eachcase.case.
.............................................................................................................................................
5
9.77 Skill check formulaformula of manganese
of manganese
species formed
type type
of of
reaction
[2]
species formed reaction
Draw
6Silver the shape of hexacyanoferrate(III) ion, [Fe(CN)6]3—
2+ Ag+, react with cyanate ions to form a linear complex.

2+ ions,
(aq) (aq)
Mn Mn + NaOH(aq)
+ NaOH(aq)
7
(ii) Suggest the formula of this complex, including its charge.
8 Mn (aq) + concentrated
2+Mn2+(aq) + concentrated HCl HCl
....................................................................................................................................... [2]

9 [S'17 P41 Q02]

Mn2+Mn
2+
(aq) (aq) + 2H
+ H 2O 2O
(aq)isomer
2(aq)
1 isomer 2
(e) 10
When heated with HCl (aq), organic isocyanates, RNCO, are hydrolysed to the amine salt,
RNH3Cl, and CO2.
11 Type of isomerism: .............................................................................................................
RNCO + H2O + HCl RNH3Cl + CO2 [5] [5]
12 [7]
1 [W'15 [W'15
P41 P41
Q03] Q03]
A 1.00 g sample of an organic isocyanate, RNCO, was treated in this way, and the CO2 produced [Total:[Total:
9] 9]
Transition Elements WS 1
© UCLES13
2014 9701/41/M/J/14
was absorbed in an excess of aqueous Ba(OH)2 according to the equation shown. The solid
4
BaCO precipitated weighed 1.66 g.
© UCLES [Turn[Turn
over over
© UCLES 2015 20153 9701/41/O/N/15
9701/41/O/N/15
1 2 The ions of transition elements form complexes by reacting with ligands.
Bilal Hameed Ba(OH)2(aq) + CO2(g) BaCO3(s) + H2O(l) Transition Elements WS 1
(a) (i) State what is meant by the terms:
Bilal Calculate the number of moles of BaCO3 produced.
(i)Hameed Transition Elements WS 2
complex, .............................................................................................................................
Transition
Transition Elements
Elements WS 1WS 1 BilalBilal
............................................................................................................................................. HameedHameed
4
ligand. .................................................................................................................................
moles of BaCO = .............................. [1]
9. 78 Skill check Complex Ions WS 2
3
.............................................................................................................................................
(ii) Hence calculate the Mr of the organic isocyanate RNCO.
1(ii) Two of the complexes formed by copper are [Cu(H2O)6]2+ and CuCl 42–.
Draw three-dimensional diagrams of their structures in the boxes and name their shapes.
[Cu(H2O)6]2+ CuCl 42–

Mr of RNCO = .............................. [1]
shape: .............................................. shape: ..............................................

© UCLES 2017 9701/41/M/J/17
2
(iii) Platinum forms square-planar complexes, in which all four ligands lie in the same plane as
the Pt atom.
3 There are two isomeric complexes with the formula Pt(NH3)2Cl 2.
Suggest the structures of the two isomers, and, by comparison with a similar type of
4 isomerism in organic chemistry, suggest the type of isomerism shown here.
Transition Elements 5 Bilal Hameed
Structures
WS 1of isomers:
Marginalizer
Transition Elements Bilal
Bilal Hameed
Hameed
6
7
Worked example 1 CN CN−
Draw the structure of the hexacyanoferrate(III) ion [Fe(CN)6]3 .
Solution Worked example 2
State the formula of each of the following complexes.
CN 3− CN−
31
NC CN −NC 27
CN− a b
Fe or Fe3+
NH3 Cl−
−
NC CN NC CN−
H3N NH3
CN CN−
Cu2+ Co2+
9.79 Skill check H3N NH3 Cl −
Cl−
Worked example 2 −
NH3 Cl
State the formula of each of the following complexes.
a b c
H H
NH3 Cl− H Cl− H
H3N NH3 N N
H H
Cu2+ Co2+ Co3+
H
H
H3N NH3 Cl− Cl− N N
H − H
NH3 Cl− Cl
H H
Solution
c
a The charge on the central ion is 2 , each NH3 ligand is neutral, and so
H H doesn’t affect the overall charge of the complex. The formula of the complex
H Cl− H is [Cu(NH3)6]2 .
N N
H H b The charge on the central ion is 2 , each Cl– ligand has a 1 charge, and so
Co3+ four ligands have a charge of 4 . Overall charge is 2 – 4 2. The formula
H of the complex is [CoCl4]2–.
H
N N
H H c The charge on the central ion is 3 , each Cl– ligand has a 1– charge, and so
Cl−
H H two ligands have a charge of 2 . Each NH3 is neutral, and so has no effect on
the overall charge.
Solution
Overall charge is 3 – 2 1. The formula of the complex is [CoCl2(NH3)4] .
a The charge on the central ion is 2 , each NH3 ligand is neutral, and so
doesn’t affect the overall charge of the complex. The formula of the complex
9.80 Skill check
is [Cu(NH3)6]2 .
b The charge on the central ion is 2 , each Cl– ligand has a 1 charge, and so
four ligands have a charge of 4 . Overall charge is 2 – 4 2. The formula
of the complex is [CoCl ]2–.80 4
c The charge on the central ion is 3 , each Cl– ligand has a 1– charge, and so
two ligands have a charge of 2 . Each NH3 is neutral, and so has no effect on
the overall charge.
Overall charge is 3 – 2 1. The formula of the complex is [CoCl2(NH3)4] .
9.81 Skill check

32
28
CO CO CO
9.82 Types
CO of Ligands
CO
Most ligands form only one co-ordinate bond with the central metal ion OC OC
in a complex.
OC OC they haveCO CO Cr
These ligands are described as monodentate because
Fe only
Fe
CO CO
‘one tooth’ with which to bind with the central cation. (The word dens in
Ni
OC Latin meansOC Ni OC OC
‘tooth’.)
OC OC
CO CO
In some cases, ligands can form CO CO
more than one bond with a metal ion
and these are described as polydentate (or multidentate).
CO CO
CO CO
OC CO CO OC
Fe Fe
Tetrahedral Tetrahedral 13.1bipyramidal
Trigonal First-rowTrigonal
d-block elements 463
bipyramidal Octahedral
(a)OC
(a) Nickel tetracarbonyl Ni
OC
Nickel tetracarbonyl Ni
(b) Iron pentacarbonyl
(b) Iron pentacarbonyl (c) Chromium hexa
OC OC
3– ■ Complex ions 2– Complexes
Figure 6.8 of 6.8
Figure transition
Complexes
– metalsof and
transition 3– CO
carbonmetals and Complex
monoxide.
■ ions
CO
carbon monoxide.2– –
CN Cl CN Cl
Cl Cl Cl Cl
NC CN A d-block metal complex ion consists of a d-block NC metal ion CNsurrounded A+d-block metal complex
by a definite number ion consists of a d-block m
Fe Co Au H3NFe Ag H3N Cl Co Au H3N
of ligands.
Cl These are molecules or negative ions CO that have a lone
CO pairof of
ligands.
electrons. These are molecules or negative ions that
Common
NC CN Cl NC CN Cl
CN
ligands Cl are
H2 water
H2 molecules, H2ClO O
HH22O, ammonia
Cl
O O
molecules, NH3, chloride
CN
ligands
ions, Cl are
Cl−,water molecules,
hydroxide
CO
ions,ClH2O, ammonia Cl CO molecul Monodentate
Monodentate
and bidentate
and bidentate
ligands liga
− C
OH , and cyanide C 9.83ions,Bidentate
C
CN .− C C C Ligands C C
Most ligands, HMost OH
O, NH
−, and cyanide ions, CN−.
ligands,
, Cl−, OH H O, −
and
NHCN , Cl−−, ,form
OH−Trigonal
only
and CN one −
, co-ord
form
octahedral The N ligandsNH
H2tetrahedral share Htheir
2N
–O
lone
square pair
NH O– empty
2 with
planar
–O
Tetrahedral
orbitalsO–linear
octahedral in theTetrahedral
central
2 The 3 ligands2 share
d-block
tetrahedral ion. their
metalTrigonal The lone
3 bipyramidal
square pair with empty
planar bipyramidal orbi
2
Examples of bidentate (a) Nickel
ligands
with the
tetracarbonyl
(‘two-toothed’)
central
(a) Nickel with
metal the
tetracarbonyl
which form
ion.
central
two
These
co-
metal
(b) ligands
Iron ion. areThese
pentacarbonyl described
(b)ligands
Iron as are
pentacarbonydesc
mono
bonds formed between the d-block metal ion and the ligands are dative covalent bonds (Chapter 4). bonds formed between the d-block metal ion and the l
3– bonds. which literally means
which
2– behaving They
‘one
literally
are
tooth’.means
sometimes – Some ‘one
called
ligands
tooth’.
coordinate
canSome form ligands
bonds.
more
The
ca
th
lig
3–
Cl
2– They are ordinate
sometimes
– bonds
calledCN with
coordinate the
Figure central
6.8 The cation
Complexes in
ligands
Figure
Cl ofcomplexes
are
transition
6.8 Complexes are:
metalsas of
Lewis
and bases
transition
carbon (electron
metals
monoxide. and carbon monoxide.
Cl donors)
pair Cl (Chapter 18). one co-ordinateone bondClco-ordinate
pair with Cl
donors) the same
bond central
(Chapter with themetal
18). sameion. central
Ligands mets
forms two NC forms forms
two
CN two + forms two
1,2-diaminoethane 1,2-diaminoethane
and the ethanedioate and the ion ethanedioate
can form two
+ionco-ocan
Co TheAu number
co-ordinate 1,2-diaminoethane,
of dative
bonds H3NFebonds
co-ordinate Ag formed
co-ordinate
bonds H32Nby
H
bondsNCHthe CHCo 2NHbonds
Cl2 ligands
co-ordinate 2with the d-blockethanedioate,
The Au number
metal ionCis2O ofknown
4dative
2— H3Nbonds Agformed H3N by the ligan
Cl bonds with the bonds
same central
with the cation
same and
centralare described
cation and as are desc
bident
Cl asClthe NC CN
Common coordination Cl
numbers asClthe coordination number. Common coordination
coordination number. Oare 4 and O 6; 2 isCl Oless common.
Cl Figure Cl6.9 Bidentate
Complexes with a coordination
ligands.
Figure
CN
6.9 Bidentate
H2 H2 ofligands.
number
C C
Cl H2 OH2 Figure
2 willtoothed’, 6.9).
be linear, those toothed’,
C CC C
with 4 are Figure
Complexes
C C
with6.9).
usually a coordination number of 2 will be
tetrahedral Monodentate
Monodentate
and bidentate
and
(occasionally square planar) and those with 6 areThe octahedral
bidentate (Figure (occasionally
ligand
The 13.15).Most
bidentate (Some square
1,2-diaminoethane octahedral
ligands, Hplanar)
Most
O, NH and
ligands,those
, Cl −
Hwith
, OH − 6 are oct
O, and
NH CN, Cl−−,
tetrahedral square planar
complexes may have distorted
octahedral
Hlinear
N
2shapes.) NH2 Htetrahedral
2N
–
O NH2 O – square
–
O planar
complexes O– ligand
may have
1,2-diaminoethane
2
distorted
(oftenlinear
3 abbreviated
shapes.)
2 (often
3 in
context to ‘en’)context uses the with the central
tonitrogen
‘en’) usesatomswith
themetal theion.
nitrogen
at central
the These
ends
atoms metal
ofligands
at ion.
the themoa
The net charge on a complex ion2–is the sum of the charge The net charge ion on a complex ion ismeans
theSomesum ofliga th
2– – CN 3–
Cl which have– aonlone the d-block
which pair haveofmetal
which aliterally
electrons,
lone and
pairtothe
means
whichofbind ‘one
literally
electrons,
ontotooth’.
a to bind‘one
central ontt
cat
Cl Cl charges on the ligands (if they are ions). The net Cl chargeClmay be positive, charges one onco-ordinate
negative theorligands
zero. one(if
bondthey are ions).
co-ordinate
with the The
same
bond net cha
centr
with
NC CN
two points. In the twocomplex
points.
Ions of
Iniontheshown
d-block
complex
metals
inhave
Figure
ion a
shown
6.10,tendency
strong
three
in Figure mo
to
Au Ions
H3NFe Ag of d-block
H3N Cl metals
+ have
Co a strong
forms twotendency to
Auform
forms forms
two complex
two ions
H N because
forms Ag two they
1,2-diaminoethaneH are
N
+
1,2-diaminoethane
and the ethanedioate and theio
1,2-diaminoethane 1,2-diaminoethane
3 attach
relatively to
small the 3 nickel
and attach
highly ion.to
charged. The
the nickel
overall
They areion.
co-ord
The
highly
Cl NC relativelyCN small and highly charged. Cl They are highly polarizing due to a high
co-ordinate bonds co-ordinate
co-ordinate
bonds bonds co-ordinate
bonds charge density,
bonds
with the bonds
same central
with the cation
same and
centr ar
Cl Cl 3– number
Cl groups is 6 and
Cl 1 and 2 are number
the shapeis 6 of
and the the complex
shape
bond formation. Ions from grb
of is the
octahedral
complex with
is oc
– CN which
CNClfavours covalent bondFigure
2– Cl formation.
6.9 Ions from
– BidentateFigureligands.
6.9 Bidentate which
ligands. favours covalent
less polarizing and form
Cl 4) with Cl ligands. angles 90°. angles toothed’,
ion–dipole
Figure
90°. bonds (Chapter 4) with 6.9).
toothed’, Figure
ligands.
6.9).
ion–dipole bonds (Chapter
NC CN tetrahedral + octahedral +
– Hsquare
NFe planar
3CN Ag 3–H
3N Cl
2– Au – Hsquare
3N
Colinear planar
Ag H3N linear
The bidentate ligand
The bidentate
1,2-diaminoethane
ligand 1,2-d(
NC CN Polydentate
Cl ligands
Cl Cl Polydentate ligands
Cl context to ‘en’)context
uses thetonitrogen
‘en’) usesatoms
the n
NC CN Cl Coammonia, chloride
+ Water, Cl and cyanide
Cl ions usually behave as monodentate
+ Water, ammonia, chloride
ligands, and cyanide ions usually beh
H3CN
NFe Ag H3N Cl Au H3N Ag H3N which meaning
have a lonethat
which
pairhave
of electrons,
a lone pairtoofbi
NC CN they form only they form
Cl one dative bond with the central d-block metal ion. A number only2+one
of larger dative
ligands arebond 2with
+ the central d-bloc
two points. In the
twocomplex
points. Inion theshown
comple in
octahedrallinear
CN
Cl
able to form two or moreCl
tetrahedral Cl with the centrallinear
dativeplanar
square bonds H2N ion and
metal 2able
CHare H2to
said form
Nto be twoCHor2 more dative
polydentate. The bonds with the central
9.84can be
resulting complexes Bidentate Ligands
very stable and are■known resulting complexesPolydentate
can be very stable and are knownena 1,2-diaminoethane
1,2-diaminoethane
attach to the nickel
attachio
■ Figure 13.15 Figureas chelates or chelating
13.15 complexes.
CH2number ismolecules
6CH
and
2number
asthe shape
is 6agents.
of
andthe
thecomple
shape
octahedral
Commonlinear
shapes of
tetrahedral
ligands are often known square planar agents. Ethanedioate
as chelating Common linear
ions
shapes and ligands are often
1,2-diaminoethane
ofof the six bonds of the known chelating
are Ethanedio
One end of the molecule willH bond with one
H angles 90°. angles 90°.
bidentate ligands, while the negative ion derived
2 from EDTA N bidentate ligands, while
(ethanediaminetetraethanoic
2 acid)theis negative ion derived from E
complex ions metal ion. The second bond N complex
is madeions 90˚ across thehexadentate,
first
NH2bond with any
NH
hexadentate, forming up to six dative bonds per ion (Figure 13.16). forming up2 to six dative bonds per ion (Fi
other remaining bonds. The bonds look like teeth hence the word
‘dentate’. H 2C H 2C
■ Figure 13.16 O O ■ Figure 13.16 H2 H2 Ni2+ O O +
Ni2O H2 H2
2+
O– O– N N
–
O– en en2+ N Ni N
C C H2C H2C C C H2N CH2 C2
H2N H2C H2CH
H2C HC
M2+ M2+ M2+ 2M2+ M2+ M2+ M2+ M
CH2 CH2
C C H2C HN
2C N C C H2C H2C
N H2 NH –
O –H2 NH2 N N
H2N
– –
O O H2 O2
O O H2 H2 O NO N NH2 H22
H2 NH
aO 1,2-diaminoethane,
The ethanedioate
– H2NCH2HCH
b The 1,2-diamino- 2 2NH2 aO CH
ethanedioate,
The C–2O42—CH2
ethanedioate
2 b The 1,2-diamino- H2
O OO O ON H 2C H2CO O O O ON
C ion acts as a
(oxalate) H2C
ethane molecule acts (oxalate)
–
C ion acts
Ni 2 + as a Ni2 +
ethane H2C en
molecule acts
– –
OC
O bidentate C C H–2NO – – OCH
CO2+ 2HO2CN C
bidentate
CH2the
ligand viaM C
as a bidentate ligand CO
ligand viaMthe
2+ as a bidentate ligand M
2+
M
CH CH
lone pairs on 2its charged via the lone pairs
CH on the
CH H C lone pairs
H C CH
on itsCH
charged
2 be
2the crab via the lone pairs
CH on
CH
C
2 Figure 6.11
Figure 6.10 The walrus,
Figure
H2CA nickel
2 Figure
2 tiger
6.11
complex The
2 and
6.10with walrus,
the
A nickel
threecrab
the
complextiger
could2 and
perhaps
Cwithofthree
molecules all could
described
perhaps
1,2 diaminoethane
molecules of 1,2 as
(en).all
‘bidentate’.
be described
H2C 2
diaminoethane as
(en)
2
oxygens the nitrogen Natoms Nin oxygens ON – N CH2 CH the nitrogen
N2 Natoms Nin
ON – N CH2 CH
CH2 2 CH N2 2 2 CH
CH
124 O 124
its amine groups H2 N O N its amine groups
NH CH CH HNH
2
Transition Elements CH2 CH2
2 2CH2Bilal Hameed
CHH 2 22
CH2 CH2 H2 2
Marginalizer – – – Bilal Hameed
–
O –
OC C O CO CO – O O OC C O CO CO
ligands CH2
(those with
ligands CH2
– Polydentate Polydentate Oseveral
(those
O po
– – –– –
–
O OC O OOCCH2 O OOOCCH
CH
C 2COO
2 O CH COO OC O
2O C
One of the most
One
commonly
of the most
encountered
commonlyis
Co Co the orientation
the orientation
shown,shown,
O
forming
forming
an octahedral
an octahedral CO
Figure 6.8 Complexes of transition metals and carbon monoxide.
shaped
shaped
complex
complex
ion ion
Figure
Figure
25.6 25.6 33
29 CO
So even
So even
though
though
water,
water,
H2 H2
H2O,H
C 2has
O,
C has
two two
lonelone
pairs
C pairs
Cof electrons,
of electrons, bothboth
O O
Monodentate and biden
Most ligands, H2O, NH3, Cl−, OH−Trigo an
are formed occur on occur on the oxygen
the oxygen atom H2atom
N so itso
would
NHit
2 would
be impossible
–
be impossible
O O –
for with
these
for these
Tetrahedral two twometal ion. These lig
s,ones,
are formed (a) Nickel the central
lone9. lone
pairs pairs
to the
form
to form
two
usuallytwo
coordinate
coordinate
bondsbonds
to the the2+Co
to Co 2+, tetracarbonyl
, whereas whereasthe two
themeans
(b) Iro
two ‘one tooth’. So
te
dioate
(calcium
(calcium
in complexes with a co-ordination
85
number of
Bidentate
four, ligands
ligands
occupy tetrahedral positions although there are a few complexes with
which literally
Figure 6.8 Complexes of transition metals and carbon m
on
efour-fold
inner co-ordination, suchlone
the inner lone
pairs
as [Pt(NH ) Cl pairs
ofhave
], that 1,2-diaminoethane
of 1,2-diaminoethane
a square
3 2 2planar are separated
are separatedand and so itsocan
oneit can
acts acts
as a asbond
co-ordinate a with the same
structure (Figure 15.15) Bidentate ligands only form octahedral complexes. forms two
forms two 1,2-diaminoethane and the ethanedi
y.they
inAs they
growwith
complexes grow bidentate ligand.
a co-ordination bidentate ligand.
number of two, the ligands usually co-ordinate bonds co-ordinate bonds
owurine
ofa urine
form outstructure
linear of
out with
of the central metal ion (Figure 15.15). bonds with the same central cation
me
xtremepain.pain.
Two common tetrahedral complexes are [CuCl4]2− and [CoCl4]2−. The
FigureCH
2
Bidentate ligands.
6.9 CH
2 H2 H2 O
toothed’, O
Figure 6.9). Monoden
elatively large size of the chloride ions, compared to oxygen atoms in water CH 2 CH 2 C C C C
The bidentate Most ligands, H
O– ligand 1,2-diaminoet
molecules, means that it is not possible for more than four ligands to fit round
he central metal ion. H2 O H2 O H2 N H2 N H2N NH2 –
O
2+ 2+ 2+ 2+ with the centra
H2 N H2 N context to ‘en’) uses the nitrogen
which have a lone pair which literally
of electrons
–
Cl
Co Co Co Co one co-ordinat
two points. In the complex ion sho
NH3
forms two forms two 1,2-diaminoeth
Pt2+
co-ordinate bonds 1,2-diaminoethane
co-ordinate bonds attach to the ni
–
number is 6 and the shape bonds ofwith
thethe
c
Cl
Figure 6.9 Bidentate ligands. toothed’, Figur
NH3 Figure
Figure
25.7 25.7
A few complexes with
a co-ordination number
NH3
angles 90°.
Cl– of 4 are planar
The bidentate
EvenEven
if theif coordination
the coordination
number
number
of a of
complex
a complex
is 4 is
or42,orwater
2, water
can can
onlyonly context to ‘en
everever
act as
acta as
monodentate
a monodentate
ligand
ligand
due due
to the
to position
the position
of the
of lone
the lone
pairspairs
of of which have a
2+
two points. In
Cr3+ electrons.
Cl
electrons.
– H2N CH2
Cl– Cu+ Cl– 1,2-diaminoet
Bidentate
9.86 Complexes with a Ligands: H2NCH2CH2NH2 complex CH2number is 6 a
Cl–
Multidentate
Multidentate
ligands
ligands co-ordination number
angles 90°.
Complexes with a Cl–Complex formed by the bidentate ligand 1,2-diaminoethane with H2
4 are usually tetrahedral Ligands
Ligands that
nickel(ii) ions.that
form
Note form
many
the use manycoordinate
of ‘en’ ascoordinate
bonds
an abbreviationbonds
for to
the a to a Nmetal
metal
ion atomatom
are areNH2
ligand.
or ion
or
called
called
multidentate
multidentate
ligands. An example
ligands.
2+
An example
of a of
multidentate
a multidentate
ligandligand
is is
H2C 2+
HN CH
EDTA 4−
EDTA 4−
. .
2 2
2+ 2+ CH
en
Ni2+ en
Types of ligand en
H2
2
CH2
Most ligands use only one lone pair of electrons to form a co-ordinate bond
N NH2 H2N
with EDTAEDTA
is anisabbreviation
NH2 the central metal ion. These ligands are described
an abbreviation
for ethylenediaminetetraacetic
H2C as monodentatefor ethylenediaminetetraacetic
H2C The The
acid.acid. structure
structure
ecause they have only ‘one tooth’ to hold onto the central cation (dens Ni2+is
en Ni 2+
2+
of EDTA
Latin for tooth). Examples ofNimonodentate of EDTA
is given
ligandsHis given
2 C in Figure
in Figure
include H 2
25.8.25.8.
O, NH 3,
en
Cl−, OH− and CN−. N H2 NH2
M N NH2 M H2
H2 N
ome ligands have more than one lone pair of electrons that can form co-
NH2 bonds with the same metal ion. Bidentate (‘two-toothed’) ligands,
ordinate CH en
HOOC–H HOOC–HC metal H HH H CH2 –COOH
orCH
example, form two dative covalent bonds 2with 2C ions in complexes.
H2N CH2 2 CH2–COOH CH2
2 en
Bidentate ligands include 1,2-diaminoethane, H2NCH2CH2NH2, the H 2C
Hthanedioate
2 Figure 15.16 Representations of a complex formed by the bidentate ligand
ion, C2O42−, and amino acids (Figure N
15.16). NC CC CN N Ni2+
1,2-diaminoethane with nickel(ii) ions. Note the use of ‘en’ as an abbreviation for the ligand. H2N CH2
complex formed by the bidentate ligand
ligand.C The 4− is particularly impressive because it
HOOC–H
ns. Note the use of ‘en’ as an abbreviation HOOC–H
for the
2 C hexadentate ligand EDTA
2 Hsix CH –COOH
CH –COOH
HH by three H bonds 2 2 Figure 6.11 The walrus,complex
the tigerOH2Cand the crab could perhaps all b
Figure 6.16 isomersitof a can
Opticalbecause form
complex formedco-ordinate with theofcentral
molecules metal ion
a bidentate Figure
in
ligand. complexes. 6.10 A nickel with three2–
molecules of 1,2 diam
DTA4− is particularly impressive
124
4− –
nds with the central metal ionFigure Figure25.8metal25.8ions that it holds them in solution
EDTA is the common O abbreviation for this ion, which binds so firmly with O C
in complexes.
– 2– and makes them chemically inactive. O CH2 N
eviation for this ion, which binds so firmly with Figure 15.17Oshows how C the hexadentate ligand can fold itself around metal C CH2
N
H2
n solution and An makes them chemically inactive.
example of a complex ion withsuchoptical isomers isoxygen
[Ni(HatomsNCH CH2NH )] ,2+ – O
hexadentate ligand can fold itself around metal
shown in Figure 6.17
9.87 Bidentate Ligands: H NCH CH NH complex
O
ions,
C
co-ordinate
as Pb2+, so
CH
bonds 2to the
CHfour
that 2
2 2 and
22 two nitrogen
2 2 3 2atoms form
4− CH
N metal ion. This is the ion formed when EDTA is
2
–O
EDTA
r oxygen atoms and two nitrogen atoms form EDTA
is usually
is usually
usedused
in alkaline
in alkaline
buffered
buffered
solution
used to treat lead poisoning. solution
to ensure
to ensure
The
CH10:03
13/04/19 it is itthe
PM EDTA is anion
the anion
Polydentate lig
–
4− ion forms such a stable complex Pb2+ –
the kidneys. OOCCH
4−
al ion. This is the ion formed when EDTA Complex is formed
with by2+the
Pb2+ ions bidentate
that they
2
ligand
can be excreted 1,2-diaminoethane
through with2 CH2COO CH2
form.
The EDTA4− ion forms such a stable complex form.
All the
All acid
the acid
COOHCOOH groups
groups
lose lose
Pb
theirtheir
hydrogen
hydrogen
ionsions
to form
to form the anion One of the mo
the anion
be excreted through the kidneys. nickel(ii) ions. Note the
The disodium saltuse
of EDTAofCH‘en’isas
4− an abbreviation
added to commercially for the ligand.
produced salad – O N H2N

4− EDTAEDTA 4− 4−dressings to extend their shelf
. .
2
of attachment
life. The EDTA4− ion traps traces of metal ionsNCH2CH C 2N H 2C
A is added to commercially produced salad – O O CH2
life. The EDTA4− ion traps traces of metal ions
that would otherwise catalyse
salt Cof EDTA4−
H 2C
en is also
N the oxidation of vegetable oils. The disodium
an ingredient of bathroom cleaners –to O help remove
–
O C
Figure –6.10 A nickel complex with th Figure 6.12.
en
the oxidation of vegetable oils. The disodium O 2+ CH
OCCH 2 CH 2 CO O
The six
The lonesix pairs
lone pairs
are shown
are shown
124
2
scale by dissolving
–
O Ca ions from the calcium carbonate left by hard water.
− help −remove
OOC–H OOC–H H HH C
H CH –COO −The ligand
− O
Each of the lone
2C 2C 2 CH2–COO
gredient of bathroom cleaners to Figure 15.17 4−
The complex ion formed by
from the calcium carbonate left by hard water. on the ondiagram.
H2NCH2CH2NHFigure
the diagram. These
6.12 The These
form
EDTAform ion.
Tip O
Figure 15.17 The complex ion formed by is coordinate
represented
2
coordinate bonds bonds
with
the EDTA4− ion with a Pb2+ ion.
the
with the therefore able t
Ni2+ the NC
N EDTA4−crystals
ion with aC C
consist the2C
of Ni
Pb2+ ion. N salt
+disodium N of ethylenediaminetetraacetic
as central
acid. Chemists
sometimes use the abbreviation Na2H2Y for the salt, where central
en metal
Y represents the 4−metal
ion. This
ion. ion.makes
This makes You will not be
en
um salt of ethylenediaminetetraacetic acid. Chemists

− − − − EDTA − EDTA
multidentate
multidentate and and
OOC–H
a2H2Y for the salt, where Y represents the 4 ion.OOC–H
2C Ligands
2C Hlike those HH in FiguresH CH 15.162–COO
CH15.17,
and 2–COO which form more than one indication of th
co-ordinate
hexadentate
hexadentate
15.16 and 15.17, whichen form more than one en bond with metal ions, are sometimes called multidentate
en
ligands, and the complexes which these ligands form are called chelates
al ions, are sometimes calledFigure Figure
multidentate 25.9 25.9
(pronounced ‘keelates’). The term ‘chelate’ comes from a Greek word for Tip
which these ligands form are called chelates a crab’s claw, reflecting the claw-like way in which chelating ligands grip O
term ‘chelate’ comes from a Greek word imaginary
for Tip
metal ions. Powerful chelating agents trap metal ions and effectively isolate Test yourse
Multidentate ligands are sometimes
claw-like way in which chelating ligands mirror grip called polydentate ligands. 2–
g agents trapisomers
metal ions Six lone
Six lone
pairs pairs
are shown them in solution.
are shown
Multidentate
on the on diagram.
the diagram.
ligands are sometimes
EDTA EDTA can can
formform
six coordinate 4− 4−
six coordinate9 Draw dot-an–
O C
17 Optical of and effectively
[Ni(H NCH CH
2
isolate
NH ) ]2+.
called polydentate ligands.
2 2 2 3
Key terms
bonds bonds
withwiththe central
the central metal metal
ion and ion and so assowell as well
O as being
as being
described
described
CH2as as
whether or n
Bilal Hameed C CH Transition Elements
multidentate,
As is the case with
Bilal multidentate, it is italso
organic molecules,
Hameed itis also
described
is the described
asymmetry asof the as hexadentate.
hexadentate.
Multidentate ligands form more than one co-ordinate bond with the same metal ion.
–
O
2
Marginalizer N a) NH3
Chelates are complex ions involving multidentate ligands.
structure
than one co-ordinate that
bond with the sameleads to
metal ion. optical isomerism as the two molecules cannot be CH2 b) CH4
ng multidentate superimposed
ligands. and are therefore spatially not the same.
Pb2+ c) CN−
Cl − ) ]+: Cl H 3N
Some complexes are linear, one
● Ifexample being ion)–Cl
the Cl−–(metal [Ag(NH
NH3bond
3 2 angle is 180°, a trans
NH3 (or E) isomer NH3
x results. Ni2+ + Ni2+ Co3+
[H3NCl➝
– Ag ➝ NH3]
HN HN 3 – 3 H3N
NH3
34 Cl NH3
Optical
A solution containing this complex ionisomerism
is called Tollens’30reagent and
–
is used in organic chemistry to distinguish
Octahedral aldehydes
complexes can from ketones.
also form optical isomers which are Cl
Aldehydes reduce the [Ag (NH +

3)2] to Ag (metallic
non-superimposable silver),
mirror while
images of each other. Optical isomerismE-isomer
can
Z-isomer E-isomer
(cis-isomer) (trans-isomer) (trans-isomer)
ketones do not. The silver forms
onlyaoccur
mirror with ona the surface ofligand
multi-dentate the test
for example 1,2-diaminoethane,
tube, giving the name of the NCH6.14
HFigure
test
9.88 CHCis–trans
2 –Bidentate
the
2
NH2. Each
silver
2
(E/Z)of
mirror
ligand the
isomers
test.NH
complexes
2
groups has a lone IIpair
of diamminedichloronickel( ) andof electrons and
tetraamminedichlorocobalt(III).
they can approach the central metal ion in a vertical plane or a horizontal
Complex ions may have a positive
The charge
shape(Figure
plane or a ion
of a complex
6.15). negative
showingcharge. In Figure
M surrounded 6.14, molecules
by three consider the bond angle between th
of a bidentate ligand and the central metal ion.
Representing the shapes of complex ions This Cl
ligand is in the
● If the −
–(metal ion)–Cl− bond angle is 90°, a
Representing three-dimensional shapes on paper can be tricky. Some horizontal plane.
These two ligands ● Ifto the Cl−–(metal ion)–Cl− bond angle is 180°, a
diagrams in this topic have thin red construction
are in the vertical
lines to help you
has/have been absorbed. For example, if a solution appea
visualise the shapes. These are notbut
plane, bonds.
twistedAnother
at colour, itresults.
way to represent is absorbing orange-red light.
90º todotted
shape is to use wedge bonds and each other.
bonds. Wedge bonds
M The come out of a transition metal ion that has formed c
d orbitals
of the paper and dotted bonds go in (Figure 8). Optical
ligands in isomerism
a complex will be affected by the ligands surro
Repulsion occurscomplexes
Octahedral between the non-bonding
can also form electrons of th
optical isome
Isomerism in transition metal complexes electrons in the d orbitals of the metal ion. Instead of bein
non-superimposable mirror images of each other. O

they only
are when the ion is isolated, the orbitals are split
occur with a multi-dentate ligand for example in
You have met isomerism in organic chemistry. Isomers are compounds
Figure 6.15 The shape of a complex ionThe
showing
closer
H2NCH Masurrounded
ligand
CH2NHcan by
get to
. Each ofthe
themetal
NH2 ion the further
groups has a lon a
with the same molecular formula but withofdifferent
three molecules a bidentatearrangements
ligand. will split. 2 2
they The amount of the
can approach splitting depends
central metal on
iontwo
in afactors
vertic
of their atoms in space. Transition metal complexes can form both
1 the plane (Figure
charge on the 6.15).
transition metal ion. An ion with a g
ftion number ofgeometrical isomers (cis-trans,This
four, the ligands usually
or E-Z
givesisomers) andpossible
rise to two opticalisomers
isomers. (Figure
attract 6.16).
the non-bonding pair of electrons on the ligand
though there are a few complexes with one with a smaller charge, so the ligand will be This pulled
edge
[Pt(NH )2Cl 2Geometrical
],transition
that have a square isomerism
planar
ligan
table – 3the metals This increases the repulsion between the non-bonding horizont
tion number Hereof two, the ligands 9.89 Bidentate
differ in their position
ligands usually
&13.1
mondentate
in space relative ligand
First-row d-block
ligand
to one another. complexes
elements
These two
and 467
ligands
the d-orbital electrons, increasing the splitt
CHEM COMPLEMENT are in the vertical
Complexes
central metal containing
ion (Figure 15.15).
This type of isomerism chelatingoccurs
agents areinusually much more
octahedral and stable than those formed 2 the size but
plane, of the ligand.
twisted at Smaller ligands can get closer to
[CuClOptical
exes arefrom monodentate
]2− and [CoCl isomerism
4ligands. This is termed the chelate effect,CH
]2−. The
and is due to an increase in CH
increasing
90º to + the
each repulsion
other. betweenM the non-bonding elec
square
4
planar complexes. Take the octahedral OH2
containing a Optical isomerism 2 2
ions, compared
entropy.Octahedral
to For
oxygen atoms
example: isomers
in water bidentate NH H N Cl electrons and increasing the splitting. Cl
+. The Cl− ligands H C H 2 O and OH 2 CH
d-orbital Th
ible for more than complex
four ligandsion
ligand can form [CrCl
to fit round
a pair of 2 (H O)
complexes
2 4 ]
In that
addition are to
2
exhibiting geometric
2
isomerism,
2
NH
2
amount of splittingClfor some common ligands is:

2 Cl N
[Ni(H 2+ 2+ 8
Cr CH2
mirror
may 2O) be6] next
images(aq) of +to6NH
each (aq)other
3other
each ! [Ni(NH
(Figure 3)6cis-
13.24).
(the
bidentate ] ligands
(aq)
orH+2Z-
N 6Hform)
such 2O(l) K = 4.0 × 10
as 1,2-diaminoethane
Br Br
—
NH2
nt [Ni(H
These 2+
2O)molecules
6] (aq) +are 3en(aq)
known !as[Ni(en) 3+
3] (aq) + 6H2O(l)
enantiomers.
(ethylenediamine) and theCo ethanedioate K = 2.0 × 1018 Cl H2OCo3+NH3 CN 13.2 Coloured complexes Co3+
or on opposite sides of the central chromium 3++ Cl CoCH2
+Cl
and
er ClwhereThis
–
form of isomerism is called optical
en represents the bidentate ligand, (oxalate) ion can show another
1,2-diaminoethane, H2N–(CHM type2Br )2of
–NH2Br . OHFor 2 example, theThechromiumNH2 of(III) ion,M 3
Crion , has
H five 3d orbita
Figure 6.15 shape a complex 2N
showing M surrou
—
ion (the trans- NH or E-form) (Figure 9). H2N NH2NH2
isomerism
2+
forms will the
■ PtFinding
(Chapter 3
rotateformula
20) because the
plane-polarized of a light
two
complex
(see in
section
13.2
ion
9.7).
Coloured
stereoisomerism, known as optical isomerism However,
Optical isomers can be
complexes three when
molecules
H2N
the
– ion
of ais
d-orbitals surrounded
have
bidentate the by
same
ligand. sixenergy
H C
water ligands,
in
NH an
2
t
split into three orbitals CHof lower energy and 2 two orbitals of h
In
equal thebutsquareoppositeplanar directions. complex identified
platin,because
the
isolated
H 2
C
their
atom,
NH2 but split into twoHsub-levels
solutions can rotate OH22N
CH in
+2 a complexCH2
2ion; the electric field of ligands
CH2
A colorimeter
− can be used to measure the concentrations may of CH
cause chemicals
the that
d-orbitals are themselves
in complexWhen This
white
ions
CH2 gives
to light
split rise
so to
falls
that two
onthe the possible
complex,
energy ofisomers
energy
an (Figure
electronis absorbed6.16
w complexes withCl ligands may be next to each other (the cis-
NH Cl OH
-ordinationcoloured or
3
which produce a coloured plane-polarized
substance during light
a (see p.
chemical 2 327).
reaction (Chapter 6). By 2
number
■ Valence bond (VB) theory transition between them lower
corresponds energy
to a photon
Figure 3.3.7 The[Co(en) d orbitals
of
two optical2Cl are
visible
isomers excited
light
of cis[Co(en)2Cl2]to a higher energy d or
are planar
or Z-theform)
following changes orinon opposite
absorbance that sides
Thetake of
twoplace the
in
different central
[Co(en)
reactions
optical
Figure
2Br2]+ rotate
involving
isomers
13.24 The the light
enantiomers formation
Cr
of of of
energy
cis-[Co(en) Brabsorbed
]+, 2]+
depends on the difference in the energ
has/have been absorbed. For example, if a solution appears to be a blue-green ■ 2 2
colouredBondingcomplex ions, a (the
colorimeter
ions can in be used todirections.
determine the formulas isof these complex
absorbingin complex 700 nm wavelengths 400 nm
it ischromium ion trans- or E-form). AThe pair ofcomplex
opposite enThe
n ions.
olour,
Figure 13.33
orange-red
shows the
light.
results of measuring the
■where
absorbance
colours
represents
of a series Hofof
complex
1,2-diaminoethane
2Oofmixtures
Theions
of
remaining
Cl of the light combine to give t
generally octahedral and has no plane
CH2NH2) CambridgeOH
The d 0.01 orbitals
If ammonia
geometrical
mol of −3
dm
is
a copper(ii)
added
transitionions,isomersto
metal
a solution
Cu2+
will
ion
containing
have
that
(aq), and has different
formed
(H2NCH
White chemical
light can
2
coordinate
−3 4−(aq). result
bonds from 4−the
with International
observed
605
is acombination
2 nm (the A Level
complementary
435Chemistry
of only red, green and bluecolour).
nm light. When equal
chromium(iii) ions, a purple 126
complex is0.01 mol
symmetry. dmtwo
Figure
The EDTA
6.16
brightnesses
Optical
structures
ofthe
these
EDTA
isomers
are mirror of
imageshexadentate
complex
of each formed
other. This by three molecules
phenomenon of
is also
are combined and projected on a screen, white light is produced (Figure 13.35).
a observed
bidentateinligand.
organic comp
igands in properties.
ligand a and
complexforms will
very For be example,
affected
stable complex by thecisplatin
ions ligands
with
chiral 3 centre is one
surrounding
d-block(see metal of
section the
ions.9.7 p.ion.
▲
325). Figure
In figure 9 The
3.3.7 cis-
there orare two optical isomers of the cis-diethylenediaminedich
formed. The chromium(iii) redion yellow
has a dgreen configuration and appears
so has three unpaired electrons. greenThis
Repulsion most occurs between
successful theanti-cancer
non-bonding electrons The
of the screen
ligand the when red595
andyellow and nm light alone overlap. 480The nm combination of red and blue
asdrugs whilst 2] . the
– + –
Cl Cu Cl
leaves two empty d-orbitals as wellion, [Co(NH
one 4s and3)4Clthree 4p orbitals Z-isomer
that can colour (top)
receive and
lone the
pairs
electrons in Complexes the d orbitals of the metal ion. light produces
Instead of being the same energy, as the bluish-red of magenta. Green and blue
Absorption produce
of lightthebygreenish-blue
[Ti(H20)6]3+ colour
trans-isomer
from the ammonia
with a
has no
molecules towhite
therapeutic
form the effect,
An example
hexaamminechromium(iii) of a complex complex ionion,with
[Cr(NH optical
) ]3+
isomers is [Ni(H NCH CH2NH )3]2+, the
called Almosttrans- O or E-isomer 580 nm
(bottom) 490 of nmthree Two 2 water ligan
intocyan. any colour can be made by
3 6overlapping light 2 colours 2 and adjusting
23
co-ordination number
hey are when the ion is isolated,magenta the orbitals cyan are split two groups. QUESTION
The transition –metals
as shown in Figure 13.25. The diagram is appropriate
shown
brightness for all
in Figure octahedral
of each – 6.17
chromium(iii)
colour. Red, green and blue560 complexes
2 in the reaction:
–
The closer abecause ligandthe can3dget to the always
electrons ion 9.
metal singly the 90 further
occupy Bidentate the d&orbitals
apartorbitals.
different Omondentate C ligandlight complexes
nm are known
500 nmas primary colours since all other
colours can be formed from them.
blue 5 a Cobalt forms a complex with the simplified
will split. The amount of splitting depends on two factors: [Cu(H 2+
2O)6] (
When O white light is shonestructure:
CH
on2a chemical substance, either asyellow-green
a solid or in solution, somesolution
CH Coloured Figure 3.3.9 Complementary
d-block compounds colours are
C
Absorbance
blue solution
15 the charge on the transition H 2N
3d
metal 2+ An ion4s
ion.
■2 Figure
CH 13.35 withlight
a greater 4p charge
–isOabsorbed2+ andwill 2
some isNreflected. opposite
energyone another onwhite a colourlight
wheel.
+
m of the
attract 2+the
Cr non-bonding
[Ar] pair of electrons
Primary
CH2 and on the ligand more
en strongly than Compounds
■ If all the light is absorbed then CH
+The of
colour of
groups a substance
en2the substance appears
1, 2
en
that
and
NH is observed
2 are
3
‘black’. typically
light absorbed
white. Similarly, com
appears pur
mplex
one with a smallerH2
charge, so the ligand will be pulled closer to this ion. zinc, one ofis the
the complementary
d-block colour
elementsof the colour
which was not classified as a tran
ers
en
are non-superimposable
N
Crform a co-ordinate
[Ar]
secondary
NH2mirrorcolours
images
Br
—
■of Ifeach
only certain 2+ Cl
wavelengths are absorbed then H2Nthe compound CI Cl
will appear coloured.
r of electrons to
This increases
bond
the repulsion between the non-bonding electrons en Cu
of the element, are that also
has been
en absorbed.
white. A characteristic property ofIfthe youtransition
now add c
ne metal
ligands arecomplexes
described
ligand and the d-orbital
h’ to hold ontoCr(NH ) [Ar]
this
H2C as monodentate
2+ occurs when there are
electrons, increasing
Ni ■ Iftwo
the splitting.
Ni2+ all or
the light is reflected then
Cr
that they the colour
CH form compounds CO of the substance
Cr
that are will appear ‘white’.
brightly coloured.blue precipitate
the central cation (dens is en 2 The ligand
ands
nodentatein a complex
ligands (Figure
include H2O,
H 2C NH3, 10).
2 the size of the ligand. Smaller ligands can get Most
closer to d-block
the metal
metal compounds
ion,
Cl are coloured, both in solution andClin the solid
H2NCH state. The
2CH 2NHcolours
2 of
– N en H N CI
mber 1 2 3N 4 5 6 7 8 9 Br— 10 O (but not all) of these compounds filled 3dCu(OH) 2(H2O
2
increasing the repulsion betweenNHthe many
non-bonding electrons of the ligand
HC is3+represented
are due to the presence of incompletely sub-levels.
Figure 3.3.11 When white
en light is shone on [Ti(H2O)6] light in the yellow-green region
H 2
en 6 complexes 2+ with sixCmonodentate ligands 2+ NH TABLE 3.3.2 SOME TRANSITION M
and 0 The
imagine 1 formation
rotating ofone
4 aco-
chromium(iii)
5of the 7 complex ion around therefore requires
2
dmlone 2
–3 pair of electrons
2that can
3 form 8 9Ni In an isolated gaseous d-block metalabsorbed
atom, strongly,
the five Ni3d
causing the solution
sub-levels
2 toallappear
havepurple.
different
as orientations[Cu(H
al
/cm
and
ion. d-orbital
3 Bidentate electrons and increasing
CH
no electronic reorganization of the d electrons. in
(‘two-toothed’) ligands, 2 the splitting. The
O
However, order
en
the of increasing
situation
– is more CHcomplicated
2 mirror
if a COMPLEXES AND THEIR en COLOUR
the two chlorine atoms are in the same position space as (shapes), but
O identical
C energies. However, in a complex ion the 3d sub-levels are orientated dee
en
amount
lent bonds of
with splitting
metal ions in for some
complexes. common ligands is: the curve represents CH 2 CH 2
10 transition metal ion has more 4 than 3 three 3d electrons, for example the iron(iii) ion,3d which has aclose to a ligand
H N CH
for Formula Colour
en
–3 2 2
dm 9H2NCH 8 2CH 72NH26 , the 5 2 1Ni(en)differently
2Br2 enrelative to the ligands. The electrons will experience repulsion and be
light The
of afirst reactio
diaminoethane, enFor
is an abbreviation
ou 3should5 be able to see that the positions of the
Hd2O
Cl (Figure
/cmacids configuration
FigureNH CNwith half-filled
15.163 Representations 3d orbitals
of a complex formed (Figure 13.26).
by the bidentate ligand O i Give theexample,
co-ordination if a number
complex in ioncomplex.
this absorbs waveleng
ino 15.16). raised in energy. The 3d electrons located further
ethane-1,2-diamine: away from the ligand
[Fe(H O) will
]3+be reduced in energy.
Yellow
concentrated am
match. The1,2-diaminoethane
best way with tonickel(ii)
be sure about
ions. Note this
the use of ‘en’
3 −3 Cu2+(aq)
as anis to■ enuse
abbreviation for the ligand.
The 3d13.34 sub-level has now blue
iicomplex
been ‘split’
Draw range
en
en
into
the two of the of
energy
stereoisomer visible
levels.
2
Octahedral
this complex.
6
light spectrum, then the ion app
3− complexes are very
t of absorbance of ten mixtures of 0.01 mol dm
For example,
6n for the the chromium (III) ion, 3d Cr , has Figure
five 3d orbitalsbecause Structure
of4p of the
the itsame energy. ion
complementary colour [Fe(CN)
in the 6]
opposite drop of
segment bythe
dropcolo
Red or
ligand. The hexadentate ligand EDTA 4− is particularly4simpressive
common and the splittingII) of the dExplain
sub-levels isthis
as shown in Figure 13.36 for the hydrated titanium(iii)
m−3 EDTA4− (aq)canthe formed between copper( ions iiiand O H
EDTA 4− C
Cr
why 3+
ions CH
[Ar]3d
is a3 stereoisomer. The pale blue pr
However, when ion is surrounded by six water ligands, the five d orbitals are 2
for the hexaaquacopper(II) 2
[CuClinion2−
to appear blued–d
it must abs
4]energy. Yellow
of form six co-ordinate bonds with the central metal ion in complexes.
e because it Fe EDTA4− is [Ar] ion. soTwo d-orbitals areimaginary
raised –in energy; three d-orbitals 2– are lowered (Different splitting
split
ons into three orbitals the of lower
common O energy
abbreviation and
for two
this ion,orbitals
which of
binds higher
firmly energy.
with b ODraw the C two
wavelength geometricalof isomers
580–595 of Ni(CN)
nm. )2The (Cl)
+ 2
2–. form the deep b
en complexes.
saidThe topeak
bemetalchiral.
ions that
Fe of absorbance [Ar]
–
They have
it holdscorresponds
them 2–identical
in solution to and makes chemical
mixing them
equal patterns
chemically
volumes are observed
inactive.
of the two in tetrahedral,
solutions,
O mirror which
Label H square
2N
the both planarand
cis-isomer
CH and NHlinear
the
[Ag(NH
complexes.
2trans-isomer. 3 2]
added.
Colourl
terms t2g and eg are
The struc
nd
o firmly with
When white light Figure falls O on the C complex, energy ligandiscan absorbed
fold used and electrons in Cthesub-levels
2
beinactive.
distinguished 15.17 shows how the hexadentate to describe
itself around metal the split
– O a 3d
CH2
Nand are based on symmetry considerations.)
2+
as by 2+,their effect on polarised light. 4− react [Co(H
ally have theions, same
O suchconcentration. Figure Hence, 6.17 copper(ii)
Optical ions
isomers and EDTA
of [Ni(H NCH inCH 1NH
: 1 molar
) ]2+ ratio
. 2O)6] in FigurePink
24.10.
ower energy Transition
d orbitals Elements
Pbare CHfour
soexcited
that 2 oxygen
to a atoms
higher and two
energy nitrogen
d atoms
orbital. form
The
2−. 4p 4− wavelength 3d Bilal Hameed
(Figure
around metal
otate the 13.34).
plane
C The formula
co-ordinateof
CH2
polarisation
bonds to the
N ■ of
metalthe
3d
Figure complex
ion.of polarised
Marginalizer
This
13.36 is [Cu(EDTA)]
4s
is the ion formed light
when EDTA is
2 2 2 2 3
4d CH2
[Cu(H
Bilal O)
Hameed ]2+
Pale blu
of energy
n atoms formabsorbed
–O
depends on theThe difference informs
the energy
Transitiona metal of the split
compounds ▲
exhibit orbitals.
Figure 10 Transition
From left tometal complexes
2 6
4− isEDTA
usedistoused
[Fe(H O) ] [Ar]in chelation
treat lead poisoning. CH10:03
13/04/19
The
PM EDTAFigure
2therapy,
splitting
4− ion3.3.8
where
of the chelating
such agents
stable are used
complex toa remove
wide
Substitutionrange of colours.
Pb2+toxic heavy
of ligandslower energy 2+
other
n
The EDTA anticlockwise.
remaining wavelengths of can
thebelight combine
right the tokidneys.
givecompounds
solutions the colour that(Ti),is vanadium (V), chromium [Cu(NH ) (H O) ] Royal b
thearebody. The ofions titanium metals CH(Cr),
with 2+
Pb ions2+that they excreted through the 3 4 2 2
metals,
able complex
observed (theThe
such
high spinas mercury,
Pb lead3d and uranium,
sub-levels in from
As is the case with that
of the
The are
heavy
organic
ligands non-identical
molecules,
in a complex
2
mirror
it
canorbitals
is
be images
the of
asymmetry
exchanged, wholly of
or the CHEMISTRY: F
mercury, complementary colour). e
abilitymanganese (Mn), iron produced
(Fe), cobaltsalad
(Co), nickel (Ni) and copper (Cu). g N cis-[Co(NH3)4Cl2] Violet
4− is added
disodium
lead and silversalt ofhave
EDTA
CHthe
the 2 titanium(
to change
to
III) ion
commercially
4−
the structure of proteins,
–
O
eachincluding
other (top) the and the structure of the
(i) What is meant by the terms bidentate and ligand?
(i) Whatforms two by the terms bidentate
is meant forms andtwo ligand?
1,2-diaminoethane and The
the ethanedio
co-ordinate bonds co-ordinate 1,2-diaminoethane attach
bonds to the nickel ion. overall c
bidentate .............................................................................................................................
bidentate .............................................................................................................................
Chapter 6 Transition elements and qualitative analysis bonds with the same central cation a
number is 6 and the shape of the complex is octahedral
bidentate .............................................................................................................................
ligand ..................................................................................................................................
Figure
ligand 6.9 Bidentate ligands. toothed’, Figure 6.9).
..................................................................................................................................
35 angles 90°.
ligand ..................................................................................................................................
.............................................................................................................................................
31
.............................................................................................................................................
The bidentate ligand 1,2-diaminoeth [2]
.............................................................................................................................................
[2]
[2]
(ii) There are three isomeric complex ions with the formula [Cr(en)2Cl 2]+.
(ii) There are three isomeric complex ions with the formula [Cr(en)2Cl 2]++.
context to ‘en’) uses the nitrogen at
(ii) There are three isomeric complex ions with the formula [Cr(en)2Cl 2] .
Complete the three-dimensional diagrams of the isomers in the boxes. which have a lone pair of electrons,
Complete the three-dimensional diagrams of the isomers in the boxes. +
the three-dimensional diagrams of the isomers in the boxes.2 two points. In the complex ion show
9.91 [Cr(en)2Cl You 2]+
Complete
may use N H2Nen. CH2
N to represent
represent
You may use N
You may use N N to
N to represent
en.
en. 1,2-diaminoethane attach to the nic
CH2number is 6 and the shape of the co
Chapter 6 Transition elements and qualitative analysis H2 angles 90°.
N NH2
Cr Cr Cr
Cr
H
Cr2C Cr
Cr Cr
Cr +
2+
Ni en Ni2+
+ 2+
H2N CH2
H2C +
CH2
N +[3]
H2 NH2 [3]
[3]
(b)
H2
Copper forms complexes with NH and en according N
to equlibria 1 and 2. NH2
3
(b)
(b) Copper
Copper forms
forms complexes
complexes with
with NHNH33 and
and enen according
according to
to equlibria
equlibria 11 andand 2.
2.
equilibrium 1
equilibrium 1
Cu2+(aq) + 4NH3(aq)
Cu 2+
(aq) + 4NH (aq)
[Cu(NH3)4]2+(aq)
[Cu(NH ) ]2+ CH
(aq) 2
equilibrium 1 Cu2+(aq) + 4NH33(aq) H2C [Cu(NH33)44]2+(aq)
equilibrium 2 Cu2+(aq) + 2en(aq) [Cu(en)2]2+(aq)
equilibrium
equilibrium 22 Cu2+(aq)
Cu 2+
(aq) ++ 2en(aq) [Cu(en) 2]]2+(aq)
2+ Ni2+ en
H2N
2en(aq) CH
[Cu(en) 2 2(aq)
(i) Write the expressions for the stability constants, Kstab1 and Kstab2, for equilibria 1 and 2.
9.92 Hexadentate ligands (i)
(i) Write
Write the
the expressions
expressions for
for the
the stability
stability constants, KKstab1 and
H constants,
C
Kstab2, for equilibria 1 and 2.
stab1 and Kstab2, for equilibria 1 and 2.
Figure 6.11
Figure The
6.10 walrus,complex
A nickel the tiger2with
andthree
the crab could perhaps
molecules all be described(en).
of 1,2 diaminoethane as ‘bidentate’.
124 A few ligands, such as EDTA (ethanediaminetetraethanoate), are
Kstab1 =
KKstab1 == they can form six co-ordinateNbonds with
particularly strong because NH2
stab1
H2
the central metal ion in complexes.
units = ..............................
units
units == ..............................
..............................
– – Polydentate ligands (those CH2 with seve
OOCCH2 CH2COO
Kstab2 =
KKstab2 == One of the most commonly encounte
H2N ions CH2
of attachment – it is hexadentate. Th
stab2
NCH2CH2N 25.9 The structure of complex
units = ..............................
– Figure –6.10 A nickel Figure units6.12.
units
complex == ..............................
with three molecules [3]
.............................. of 1,2 diami
Types of ligand OOCCH2 CH2COO DEFINITION [3]
[3]
124
Most ligands form only one co-ordinate bond with the central metal ion in a A polydentate ligand is one Each of the lone pairs is able to form a
UCLESFigure
complex. These ligands are©described 6.12 The
as monodentate EDTA
(orEDTA ion. 9701/42/M/J/17which forms two or more
4− because
unidentate)
they have only ‘one tooth’©with
©UCLES
2017
which to bind with the central cation. (The
UCLES2017
2017 9701/42/M/J/17co-ordinate bonds with the central
9701/42/M/J/17
therefore able to attach in six places.
word dens in Latin means ‘tooth’.) metal ion in a complex.
hexadentate
In some cases, ligands can form more than one bond with a metal ion and
ligand You will not be expected to draw ions
these are described as polydentate (or multidentate). Examples of bidentate
ligands which form twoCEDAR COLLEGE
co-ordinate bonds with the central cation in complexes indication of the variety
TRANSITION ELEMENTS WS 1 of complexes
are ethanedioate, C2O42–, 1,2-diaminoethane, H2NCH2CH2NH2 and amino
acids such as glycine (Figure 25.13).
9.93 Hexadentate ligands H O

O= O O Test yourself
− −
O
− C−C = H2NCH2CH2NH2 H−C−C = 2– –
=
– –
−
–
− O−
O O
The [EDTA] ion bound to
4— a O −metal
central OC
ionH in an octahedral O= C−
N
coordination complex. H
9 Draw dot-and-cross diagrams of eac
−
H – −C −
O CH2 −
CH2
−
O CH2 N
ethanedioate glycine 1,2-diaminoethane whether or not they can behave as a
Cu2+
−
C CH2 –
O− CH
− 2
–
O N a) NH C − CH − N − 2
CH
3
O= O
−
2
=
– −
C − CH2 CH2 − C =
–
b) CH CH2 O O
– CH2
4
−
−
O
−
O −
C
NCH2CH2N
O 2+
Pb c) CN −
=
O=
−
−
C − CH2 CH2 − C = O
– − O
– −
d) CO
O
EDTA CHFig 25.14 The complex ion formed by EDTA
2 a Cu ion. EDTA binds cations so
with
strongly that it can be10 Predict
used sparingly
2+
F28
as an the likely shape and bond an
Fig 25.13 Three bidentate ligands and the hexadentate ligand EDTA 2+
antidote to lead poisoning by trapping Pb
are particularly N the shelf life of manufacturedthe complex ion, clearly show the lo
– ions. It is also used as a means of extending
O
A few ligands, such as EDTA (ethanediaminetetraethanoate), foods, such as
strong because they can form six co-ordinateCbonds with the centralHmetal C salad dressings, by trapping metal ions which
would catalyse the oxidationco-ordinate bonds. State the oxidati
2
ion in complexes. EDTA binds so strongly with metal ions that it makes them of vegetable oils
chemically inactive (Figure 25.14). O CH2
–
O C complex.
The complex ions which form between polydentate ligands and cations are DEFINITION
known as chelates (pronounced ‘keelates’). This name comes from the Greek
A chelate is a complex ion in
a) [Ag(CN)2]−
word chelos meaning ‘crab’s claw’. In these complexes the ligand formsO a
Bilal pincer-grip
clawlike Hameedon the central metal ion. which each ligand forms b) two [Co(NH
or ) Cl]2+ Elements
Transition
3 5
Bilal Hameed 6.13 The
more co-ordinate Marginalizer
bonds with the
In general, polydentate ligands are Figure
more powerful than complex ion formedcentral
simple monodentate by metal ion. c) [NiCl ]2−
4
ligands. The stability of a complexEDTA with a Pb ion. The ligand can fold
ion is enhanced by 2+
chelation as the
pincer-grip of the polydentate ligand can hold the central metal ion more d) [Fe(CN) 6
]3−
securely. Even if one of the bondsitself around metalstill ions, such
metalas Pb , so
2+
is broken, the others hold the
CH2 ligands use only one lone pair of electrons to form a co-ordinate bond
Most O OC C 4C CO O
–
S C N Some ligands are known as ambidentate ligands. An ambidentate ligand hasform two lone pairsOpure nickel (Mond process). O
extremely
with
NH2 the central metal ion. These of ligands
electrons,are
for described
H2Ctheasthiocyanate
example monodentate
ion –
2+ (Figure 13.21). Hence it can form a dative
OC via
O 2+ bond O O O C O –
Ni is en Ni
Deducing
because they have only ‘one
■ Figure 13.21 tooth’
thetosulfur
hold oronto the central
the nitrogen. cation
Other (dens
examples of ambidentate ligands include the nitrite ion, NOthe−, total charge given the formula of the ion and lig
2 CH2
Latin for tooth). One
Examples ofNimonodentate ligands include H2O, NH3, CH2
Ni
ne dative
2+
en
resonance 2+ and the cyanide ion,HCN
2C −. The total or net charge on a complex depends upon the number of ligands, their c
Cl−, OH− and CN −. N CH2 CH2 N
structure for the Transition metal atomsNmay also form complexes via dative bond formation. oxidation
The extraction
state of the central transition metal ion to which the ligands are bonded
ith a
thiocyanate ion of nickel involves the formation
H
36 NH2 of a transition metalorcomplex.
and thermal decomposition CH
net charge on
464 13 The periodic table – the transition metals
CH2
a complex can be deduced from its composition and the oxidatio
x. Some ligands have more than one lone pair of electrons that 2
can form co-
Nickel is usually extracted from its sulfide ore. This isCH 32to give nickel(ii)
roasted in air O oxide,
central C NiO,
cation.
2
enThe oxidation state of the central ionCcan beO deduced from the for
– –
NH2 bonds with the same metal
ordinate ion. Bidentate (‘two-toothed’) ligands, 2
ative which is then reduced by carbon to the impure metal. Refinement (purification)Ethanediaminetetraethanoic
ofcan
thebe achieved
complex. O acid (Figure 13.17),
O usually just called EDTA or H4E
forCH
example, form two dative covalent bonds
by reaction with metal ions in complexes.
H2N 50 °CCH
with carbon monoxide at about and
2 normal pressure, which results in the
with a 2 en widely used chelating agent (Figure 13.18). It is present in shampoos (Figure 13.1
Bidentate ligands include 1,2-diaminoethane, H2NCH2CH2NH
formation of tetracarbonylnickel(0), 2 , the4. This complex is easily thermally decomposed
Ni(CO) c The EDTA4– ion acts as a hexadentate ligand, using lone pairs on
tosoft drinks containing ascorbic acid and sodium benzoate to preve
x. Worked
cosmetics example
and
H2N CH
ethanedioate
2
2−
ion, C2O4 , and amino
formacids (Figure
extremely Figure
15.16).
pure 15.16 Representations
nickel (Mond process). of a complex formed by the bidentateboth
ligand
its nitrogen atoms and its charged oxygens
benzene. It
1,2-diaminoethane with nickel(ii) ions. Note the use of ‘en’ as an abbreviation forischarge
also
the used as a preservative in foods and cosmetics. EDTA is also us
ligand.
Deduce the on the tetraamminedichlorochromium(III) complex ion. What is its formu
esentations of a complex formed by the bidentate ligand Deducing the total charge given the formula of the ion and ligands therapypresent
to remove harmful heavy metals or their ions from the body.
with nickel(ii) ions. Note the use of ‘en’ as an abbreviationThe
for the ligand. 9.94 Hexadentate ligands
The hexadentate ligand - EDTA
EDTA ■4−Figure 13.17
is particularly impressive
total or net charge on a complex depends upon the number of ligands, their charge and the
The sodium salt of
The because
formula has it chloride ions, Cl−, and four ammonia molecules, NH3, so the ligand
two
O has an oxidation number of +3,
can formtransition
six co-ordinate two negative charges (−2). The central chromium cation
oxidation state of the central metal ionbonds
to whichwith
10 the
the central metal ion total
ligands
Deduce the are bonded. The
in complexes.
the total or net charge2–
te ligand EDTA4−
is particularly impressive because it EDTA4−can is the common
EDTA
abbreviation for charge
this
contributes three positive charges (+3). Hence
– on the complex io
or net charge on a complex be deducedO from its composition
total and ion,
the which binds
oxidation
and state so firmly
of the
formula
with O (NH ) ]+.
is therefore [CrCl O C
o-ordinate bonds with the central metal ion in complexes. 2 3 4
–
als central cation. The metal ionsstate
oxidation that
–
it
of holds
the them
central ionin solution
can2–be and
deduced
formulas makes
offrom
the them
the chemically
formula and inactive.
charge – O 2 CH2
common abbreviation for this ion, which binds sooffirmly with
the complex. Figure 15.17Oshows how C 829055_13_IB_Chemistry_451-488.indd
the hexadentatefollowing complex
ligand
463
can fold Deduce
itself around O
metal
the oxidation stateCof copper in CH
C the [Cu(CN) 3−
4]2 complex ion. What is its name?
t holds them in solution and makes them chemically inactive. O such as Pb2+, so that CHfour
ions: a nickel(II) ion O atoms form –O
CH N
ions, 2 oxygen withatoms
six ammoniaand two nitrogen 2
ows how the hexadentate ligand can fold itself around metal C CH2 C
The complex ion
4− CH
is an2 anion with a total or net charge of −3. CHThe
2 formula has four cyan
Worked
2+, so that four oxygen atoms and two nitrogen atoms form example co-ordinate
– O
bonds to the
N metal ion. This
ligands,is the
and aion formed when – as
O EDTA
ligands which is
contributeN a total of four negative charges (−4). Hence the central copp
4−II) ion 2+
4− charge
used to treat lead poisoning. CH2
13/04/19 The
10:03 PM EDTA
copper( forms
ion with such a stable
contributecomplex
one positive charge CH
so its
2
Pb
oxidation state is +1. This ion is the tetracyanocupr
nds to the metal ion. This is the ion formed when Deduce EDTAthe is on the tetraamminedichlorochromium(
with Pb2+ ions2+that they can be excreted
III) complex
fourion. What ions.
chloride
through
is its formula?
the kidneys. 2+ CH2
4−
ad poisoning. The EDTA ion forms such a stable complex Pb 11 Find about Cu
The formula has two chloride ions, Cl−, and four ammonia 4− molecules, NH3,the so the ligands contribute
that they can be excreted through the kidneys. The disodium salt of EDTA is added
mechanism to of commercially produced salad – O CH2
two negative charges (−2). The central chromium CH cation
2 has an oxidation number of +3,■
4−
so itIsomerism in complex ions H2C N
4−
10 Deduce the contributes threedressings to extend
positive charges theirtheshelf
(+3). Hence totallife.
or netThe EDTA
action
charge onof the ion traps
cisplatin
complex traces
ion is +1. Theof metal ions C
salt of EDTA is added tototal commercially
charge and produced salad –
that[CrCl
would N and outline any – ON CH2
O 2(NH3)otherwise catalyse the oxidation of vegetableCis–trans
oils.
O The disodium
formula is therefore +
4] . isomerism –
end their shelf life. The EDTA 4− ion of
traps
the traces of metal ions H 2C changes that occur C H2C O C
salt C
formulas
of EDTA4− is also an 3−ingredienttoof the bathroom
complex ion cleaners
Where
to help remove
a complex ion containsCH two 2 different ligands, it can exist as two isomers in w
following complex Ostate of copper O
erwise catalyse the oxidation of vegetable oils. TheDeduce disodium
the oxidation
scale by dissolving
– Ca 2+ CH
in the [Cu(CN) 4] 2 complex ion. What is its name?
ions from the calcium
its use carbonate left byarrangements
hard– water.
ions: a nickel(II) ion O C during as an
different O ofCthe ligands (Figure 13.22).OThis is termed cis–trans isomeri
is also an ingredient of bathroom cleaners to help remove anti-cancer agent. Figure 15.17
ng Ca 2+ ions from the calcium
with six ammonia
carbonate
The complex ion is an anion with a total or net charge of −3. The formula has four the relative positions of the two ligands.The
cyanide ions acting Cis complex
means same ion formed by means opposite s
side, trans
and a left by hard water.which contribute
ligands,
copper(II) ion with
as ligands Tip a total of fourOnegative charges (−4). Hence the central copper ion must Othe EDTA4− ion with a Pb2+ ion.
of isomerism is only possible for complex ions with coordination numbers greater th
contribute oneFigure
positive15.17
chargeThe
so complex ion state
its oxidation formed byThis ion is the tetracyanocuprate(
is +1. I) ion. 13.18 The [Cu(EDTA)]2− complex
■ Figure ■ Figure 13.19 Shampoos oft
four chloride ions. [Pb(EDTA)]
crystals
the EDTA4− consist
ion with a Pb2+of 2—
the disodium salt of ethylenediaminetetraacetic
ion. [Cu(EDTA)]
The cisacid.
complex [PtCl2(NH2—
Chemists 3)2], systematic name cis-diamminedichloroplatinum(ii),
4−
cisplatin (Figure
− 13.23) and is used in chemotherapy for EDTA
treatingion which helps softe
certain types of can
11 Find about the sometimes use the abbreviation Na2H2Y for the salt, where Y represents the 4 ion. complexing calcium ions pres
nsist of the disodium salt of ethylenediaminetetraacetic
mechanism of acid. Chemists isomer, known as transplatin, has no anti-cancer properties.
he abbreviation Na2H2Y for the salt,action
whereofY cisplatin
■ Isomerism in complex ions
represents the 4− ion.
and outline any
Ligands like those in Figures 15.16 and 13.22
■ Figure 15.17, which form ■a Ligand
more than replacement
one +reactions
b +
co-ordinate
Cis–trans isomerism bond with metal ions, areisomerism
sometimes called NH3 NH
changes that occur Cis–trans All themultidentate
stable, simple d-block metal ions exist in water in the3 hydrated form whe
ose in Figures 15.16 and 15.17, which form more than one
to the complex ion Where a complex ion containsand
ligands, the complexes
two different ligands, itwhich
caninexistthese ligands
as two
a transition metal form
isomers are called
in which
metal there chelates by six octahedrally arranged water molecules. For examp
ion isare
surrounded
nd with metal ions, are sometimes during its usecalled
as an multidentate Cl word NH3 Cl NH
anti-cancer agent.
different arrangements (pronounced
of the ligands‘keelates’). TheThis
(Figure 13.22). term ‘chelate’
iscomplex
termed comes
cis–trans
ion from
isomerism, a referring
Greek
copper(ii) to Cu2+for
ion, Tip accurately represented
(aq), is more by [Cu(H2O)6]2+3 .
he complexes which these ligands form are called chelates
the relative positionsa ofcrab’s
the two claw,ligands. Cis means
reflecting thesame side, trans
claw-like waymeans oppositechelating
in which side.IfThis formammonia
aqueous
ligands Cogrip solution is added to a solution of aCo copper(ii) salt, a proce
is onlyTip
eelates’). The term ‘chelate’ comes from a Greek word for Cambridge International A chelating
Level Chemistry Multidentate ligands are sometimes
of isomerism possible
metal for complex
ions. Powerful ions with coordination
agents trap numbers
metalgreater
ionsthan or equal
Cl to 4.
replacement
and effectively (Figure 13.20)
isolate NHoccurs; four of the water molecules are replaced
Cl by am
H3N
as changes fromcalled lightpolydentate
blue to darkligands.
3
eflecting the claw-like way in which chelating The ligands grip [PtCl
werful chelating agents trap metal ions and effectively
cis complex
isolate 9.95 Types of Ligands
cisplatin (Figure 13.23)
2(NH
them in3)2solution.
Multidentate ], systematic
ligands arename
andpolydentate
cis-diamminedichloroplatinum(ii), and
sometimes
is used in chemotherapy
is known
the colour
for treating certain types of cancer. The trans 2+NH
blue:
called ligands. [Cu(H2O)6] (aq) 3 + 4NH (aq) → [Cu(H O) (NH ) ]2+NH
3 4 (aq) + 4H2O(l)
3
n. isomer, known as transplatin,
Figure Key
24.5 shows hasshape
terms
the no anti-cancer
of complexesproperties.
with four ligands. CH2
3
2+
2 2
■ Figure 13.22
Ligands are of three types that have three different coordination blue
NH
H2C cis-[Co(NH
2 +
dark blue
+
+ + 3)4Cl2] trans-[Co(NH3)4Cl2]
a ■
2– b
NH3 Multidentate ligands form more than one Cl
NHco-ordinate
2–
Cis–trans isomerism numbers.
NC

CN 3 bond withIfthe
EDTA H Nismetal
same added toNH
ion. the dark blue solution of tetraamminediaquacopper(ii)
blue-violet 2 green
2
ions,
St
in a transition metal and water molecules areCHreplaced
2 by the hexadentate ligand to give a pale blue so
ands form more than one co-ordinate bond with the same metal ion. Chelates are complex ions involving multidentate ligands. Co
complex ion Cl
• Monodentate
NiNH
ligand forms
Cl
3
Co
NH
one dative
■ Figure 13.20
Ligand exchange
covalent (co-ordinate)
EDTA
HN
(aq) + [Cu(H bond
CH O) (NH ) ]
3 4−
2
2
2 3 4
2+(aq) → [Cu(EDTA)2−](aq) + 4NH3(aq) +
mplex ions involving multidentate ligands. Co Cl Co NH
with a central
CN metal ion in a complex.
2
NC
reactions. From top dark2 blue pale blue
Cl NH3 Cl
H3N Cl
to bottom: copper(II)
Cl H2C NHNH
3
2
• aBidentate The increase in entropy (Chapter 15) accompanying the replacement of six mon
Cl CH2
[Ni(CN) ] ligand bforms
4
2–
two
[CoCl ] dative
ions, copper( covalent
4
2–
) ions (co-ordinate)
by onePt
hexadentateII bonds with
ligand accounts for the high degree of stability of EDTA com
2+
NH3 NHaddition [Co(en) ]
a central metal ion in a complex.
829055_13_IB_Chemistry_451-488.indd 3
after 3 of466 the
Figure 24.5 The complex ion formed between a transition Cl use of EDTANH3 in the 15.8titration
The of metalofions.
shapes complex ions 433
concentrated aqueous
Figure 24.6 [Co(en) 2+ is an example of a complex ion
If a3]solution of a copper(ii) salt is treated with an excess of concentrated hydr
• Hexadentate ligand forms 6 dative covalent (co-ordinate) bonds with
metal ion and+a larger ligand can only fit four ligands around + containing the bidentate ligand NH CH CH NH (abbreviated
cis-[Co(NH 3)4The
Clion.
2] shapes
433 ammonia, cobalt(II)
3)4Cl2]
Figure 13.23
either atrans-[Co(NH
■ acid, the water molecules 2are2 replaced in a similar ligand replacement reaction. T
the 15.8
central ofarranged
These are complex in ions square planar 2 2
blue-violet to ‘en’). Structure of cisplatin
greencobalt(II) ions
shape (as in a [Ni(CN)4]2–) or a tetrahedral shape (asions, molecules are replaced by four chloride ions to form a yellow complex ion:
a central metal ion in a complex.
b [CoCl4]2–).
in
after the addition
[Cu(H2O)6]2+(aq) + 4Cl−(aq) → [CuCl4]2−(aq) + 6H2O(l) 13/04/19 10:03 PM
• Multidentate/polydentate ligand forms more than one co-ordinate
469983_15_Chem_Y1-2_418-449.indd 433 of concentrated
All ligands can donate an electron pair to a central hydrochloric Note in Table 24.4 that blue
acid the charge on a complex is simply yellow
bondmetal with ion. the same metal numberion.
433 13/04/19 10:03 PM
transition The co-ordination of a the sum of the charges on the central metal ion and on
complex is the number of co-ordinate (dative) bonds to the each ligand in the complex. Some complexes will carry no
central metal ion. Some ligands can form two co-ordinate charge, e.g. Cu(OH)2(H2O)4.
829055_13_IB_Chemistry_451-488.indd 466 18/05/15 10:38 am
bonds from each ion or molecule to the transition metal +
ion. These are called bidentate ligands, as shown in Figure H H
24.6. Most ligands, such as water and ammonia, form just H N Ag N H
one co-ordinate bond and are called monodentate ligands. H H
372
A few transition metal ions, e.g. copper(I), silver(I), Figure 24.7 The diamminesilver(I) cation has a linear
gold(I), form linear complexes with ligands. The structure.
co-ordination number in these complexes is 2
(Figure 24.7). Table 24.4 shows some common ligands.
9.96 Ligands 829055_13_IB_Chemistry_451-488.indd 464
Name of ligand Formula Example of Co-ordination Shape of complex

complex number
water H2O [Fe(H2O)6]2+ 6 octahedral (see Figure 24.4)
ammonia NH3 [Co(NH3)6]3+ 6 octahedral
chloride ion Cl– [CuCl4]2– 4 tetrahedral (see Figure 24.5b)
cyanide ion CN– [Ni(CN)4]2– 4 square planar

(see Figure 24.5a)
hydroxide ion OH– [Cr(OH)6]3– 6 octahedral
thiocyanate ion SCN– [FeSCN]2+ or

[Fe(SCN)(H2O)5]2+ 6 octahedral
ethanedioate ion (abbreviated as –OOC COO– [Mn(ox)3]3– 6 octahedral

‘ox’ in the formulae of complexes)
1,2-diaminoethane NH2CH2CH2NH2 [Co(en)3]3+ 6 octahedral (see Figure 24.6)

(abbreviated as ‘en’ in the formulae
of complexes)
Table 24.4 Some common ligands and their complexes.

37
33
9.97 Skill check

What is the oxidation number of the transition metal in each of the
following complexes?
i [Co(NH3)6]3+
ii [Ni(CN)4]2–
iii [Cr(OH)6]3–
iv [Co(en)3]3+
v Cu(OH)2(H2O)4
9.98 Complex ions

A simple formula does not make it clear which groups are attached to
the metal ion, it is common practice to enclose the complex ion in
square brackets.
An example of this is Cr(H2O)6Cl3, which does not make it clear which

ligands are attached to the chromium ion.
It could, for example, be [Cr(H2O)6]Cl3 (which has no chlorine ligands

but has three free chloride ions) or
[Cr(H2O)5Cl]Cl2.H2O (which has one chlorine ligand and two free

chloride ions).
9.99 Stereoisomerism in complexes

Because of the three-dimensional shape of complex ions and the
positions of ligands around the central metal ion, isomers can occur in
four co-ordinated and six co-ordinated complexes.
Isomers are compounds with the same formula, but different

arrangements of their constituent atoms.
Transition metal complexes can form both geometrical isomers (cis-

trans) and optical isomers.

EDTA with a Pb2+ ion.Pb The ligand can fold
itself around metal ions, such as Pb d)d)CO[Fe(CN)
● cis–trans (E/Z) ]3−
6 isomerism
CH2, so
2+
that four oxygen atoms and two nitrogen 10 Predict the likely shape and bond angle in each of th
● optical isomerism.
–
atoms Oform co-ordinate bonds N the
to the complex ion, clearly show the lone pairs of elec
C 38 H2C 34 co-ordinate bonds. State the oxidation state of cent
metal ion.
O
This is the ion formedCH
EDTA is used to treat–
when
2
O lead poisoning.
C The Cis–trans
complex. (E/Z) isomerism Stereoisomerism of complex
EDTA forms such a stable complex with Isomerism
The [Ag(CN)
a)square is2]commonplace
−
planar structure ofin [Ni(NH
organic )compo
Cl2] a
O and same
result
b) structural
of the
[Co(NH formula,
+spatial
) Cl]2+ but have
positions a different
around
3 2 arran
a centra
Pb2+ ions that it can be excreted through [Co(NH3)4Cl2]3 5falls
Stereoisomerism giveinto
riseone
to of
cis–trans (E/Z) isom
two categories:
the Figure 6.13 The complex ion formed by
kidneys. co-ordinated
c) [NiCl4]2− complex ions can also have ster
9.100 Stereoisomerism 2+ in can
EDTA with a Pb ion. The ligand complexes
fold d) [Fe(CN) ]3− defines compounds that hav
(E/Z)
● stereoisomerism
cis–trans 6 isomerism
2+
itself around metal ions, such as Pb , so
Square planar complexes
that four canand
exhibit cis-trans ●IIisomerism.
Diamminedichloronickel(
oxygen atoms two nitrogen ) optical isomerism.
Tetraammine
atoms form co-ordinate bonds to the
Cl–
metal ion. This is the ion formed when
EDTA is used to treat lead poisoning. The Cis–trans (E/Z) isomerism Stereoisomerism of complex ions
and same structural formula, but
EDTA forms have
– such a a different
stable complex arrangement
with –The
the
in
Isomerism
square trans-form
space.
is commonplace
planar structure of in H
organic
[Ni(NH )compounds.
Cl ] and theHo
Cl Cl 3N 3 2 2
Stereoisomerism falls into onethat
Pb ions
2+
of ittwo
can becategories:
excreted
NHthrough
3
result of the spatial
[Co(NH3)4Cl2] giveNHrise
+ positions
3
around a central
to cis–trans (E/Z) isomerismcation(
the kidneys. 2+ co-ordinated
2+ complex ions can also have 3+ stereoisom
Ni Ni Co
● cis–trans (E/Z) isomerism
Cl– stereoisomerism defines compounds that have the sa
H3N H 3 N H
NHDiamminedichloronickel(
3
II) Cl– Tetraamminedichloroco
NH3
the cis-form Cl–
Cl–
Cis–trans (E/Z)
and same isomerism
structural formula, but have a different arrangement
Z-isomer
Cl
in space.
Cl E-isomer – –
H 3N E-isomer
Stereoisomerism falls into one of two categories:
(cis-isomer) NH3 (trans-isomer) NH (trans-isomer)NH3
The square planar structure of [Ni(NH ) Cl ] and the
Ni2+ 3 2 2 Ni2+ of Co octahedral structure3 3+
[Co(NH●3)4cis–trans (E/Z)
Cl2] + give riseisomerism
FigureCl–to
6.14 Cis–trans(E/Z)
cis–trans (E/Z) isomerism
isomers
H3N of (Figure 6.14).
diamminedichloronickel(II)
H3 N and tetraamminedichlorocobalt(II
H3N
NH3 Cl– NH3
In Figure 6.14, consider the Clbond
– angle betwee
Diamminedichloronickel(II) Tetraamminedichlorocobalt(IIIand
) the central metal ion.E-isomer
Cis–trans (E/Z) isomerism
Z-isomer E-isomer
The square planar structure(cis-isomer)
–
ofCl[Ni(NH (trans-isomer)
) Cl ] and the octahedral –
●ClIf structure of
the Cl−–(metal
(trans-isomer)
ion)–Cl− bond angle is 90
9. 101
+ Stereoisomerism
[Co(NH3)4Cl2] giveFigure
rise to cis–trans
6.14
3 2 2 in complexes
Cis–trans(E/Z)
(E/Z) isomerism (Figure 6.14).
isomers of diamminedichloronickel(II) and tetraamminedichlorocobalt(III).
Cl– H 3N H3N ● If the Cl− –(metal ion)–Cl− bond angle is 18

Octahedral complexes can exhibit cis-trans isomerism with
NH3 NH3 NH3 In Figure 6.14, consider
results. NH3 the bond angle between the t
monodentate ligands or optical isomerism with
Co3+ Tetraamminedichlorocobalt(IIIand
bidentate
3+
central ligands.
metal ion.
2+
Ni2+ II)
Diamminedichloronickel( ) Cothe
H3N H3N Cl– H3N –

NH3 Cl– NH3 Optical
●ClIf
isomerism
theClCl– –(metal
−
ion)–Cl bond angle is 90°, a cis (
the trans-form
−
H3N ●Octahedral complexes

If the Cl−–(metal ion)–Clcan also
bond form
angle optical
is 180°, is
a tra
−
Cl– Cl– H 3N
Cl–
NH3 NH3 NH3 results.

NH NH
Co3+
non-superimposable
Co3+
3 3 mirror images of each oth
Ni2+ Ni2+
mer E-isomer
H3N (trans-isomer) H3 N
E-isomer only occur with a multi-dentate ligand for exa
Z-isomer
H3N
mer) NH3 Cl – (trans-isomer)NH3 Optical
(cis-isomer)
H NCH 2
isomerism
Cl– CH NH . Each of the NH groups has a
2 2 2 2
trans (E/Z) isomers of diamminedichloronickel(II) andthe cis-form
tetraamminedichlorocobalt(
Cl–
III). Octahedral complexes can
they can approach the also formmetal
central opticalion
isomers
in a vw
NH3
non-superimposable mirror images of each other. Opt
plane (Figure 6.15).
Z-isomer
In Figure
E-isomer
6.14, consider the bond E-isomer only occurligands
Z-isomer
angle between the two(cis-isomer)
chloride with a multi-dentate ligand for example 1,2
(cis-isomer) (trans-isomer) (trans-isomer) H2NCH2CH2NH2. Each of the NH2 groups has a lone p
and the central metal ion.
re 6.14 Cis–trans (E/Z) isomers of diamminedichloronickel(II) and tetraamminedichlorocobalt(III). they can approach the central metal ion in a vertical Thisp
hor
● If the Cl− –(metal ion)–Cl− bond angle is 90°, a cis (or Z) plane (Figure
isomer
These 6.15).
forms.
two ligands
In Figure 6.14, consider the bond angle between the two chloride ligands
are in the vertical
● If theandClthe
− central metal ion.
–(metal ion)–Cl− bond angle is 180°, a trans (or E) isomer
plane, but twisted at This ligand is
90º to each other. M horizontal pla
results.
● If the Cl− –(metal ion)–Cl− bond angle is 90°, a cis (or Z)These
isomer forms.
two ligands
are in the vertical
● 102 Square
9.−–(metal
If the Cl planar:
ion)–Cl− bond anglecis-trans isomerism
is 180°, a trans (or E) isomer
plane, but twisted at
Opticalresults.
isomerism 90º to each other. M
For a complex with two ligands of one type and two of another type in
Octahedral complexes can also form optical isomers which are
the square plane, like platin, Pt(NH3)2Cl2, there are two different
Opticalarrangements
non-superimposable isomerism
mirror images of each other. Optical isomerism
possible of these ligands around three
Figure 6.15 can
the central
The shape of a complex ion showing M su
ion.
of a bidentate ligand.
only occur with acomplexes
Octahedral multi-dentate ligand
can also for example
form optical isomers1,2-diaminoethane,
which are molecules
H2NCHnon-superimposable
CH NH . Each ofmirror
the images
NH of each
groups has other.
a Optical
lone pair Figure
isomerism
of electronsTheand
6.15 can Stereoisomerism
shape in co
of a complex ion showing M surrounded
2 2 2 2 Cl NH
onlyapproach
they can occur withthe a multi-dentate
central metal ligand
ion for
in aexample This
three
agives
3 molecules
vertical1,2-diaminoethane,
plane or rise
horizontal a to
ofSome two
bidentate possible
complex isomers
ligand. ions (Figuree
can show
H NCH
plane (Figure
2
CH
2 6.15).
2
NH2
. Each of the NH 2
groups has a lone pair of electrons and
they can approach the central H3Nmetal Cl a verticalClplaneThis
Ption in Ptor agives
Cl rise toSquare
horizontal two possible
planar isomers (Figure 6.16).
complexes can sh
plane (Figure 6.15).
NH3
This ligand is in the NH3 Octahedral complexes can show
horizontal plane.
126
These two ligands the cis-form This ligandthe is in trans-form
the or optical isomerism with biden
the ‘cis’ form horizontal the
plane.‘trans’ form
are in the vertical
These 126
two ligands
plane, but
are twisted at
in the vertical Z isomer E isomer
90º to each
plane,other.
but twisted at
E-Z isomerism in square pl
M
90º to each other. Figure
M 25.18 This occurs in planar complexe
Figure 25.18. There are two dif
Transition Elements and Bilal
chloride ions could arrange
Hameed
FigureThe
Figure 6.15 6.15shape of a complex
The shape ionion
of a complex showing
showingMMsurrounded by
surrounded by The two structures drawn are is
three molecules of a bidentate
three molecules ligand.
of a bidentate ligand. superimposable. This is the key
Ionization isomerism occurs in transition metal complex compound in which
the elements are the same but the identity of the cation–anion pair varies. For
25.9 The structure of complex ions
example, [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br are the same compound, but
the sulfate and bromide ions have39exchanged positions, thus changing the
35 is, they are ionization isomers.
charge on the cation; that
DEFINITION
l metal ion in a A polydentate ligand is one
dentate) because which forms two or more Br− 2+ OSO3 +
al cation. (The co-ordinate bonds
H3N with the central
NH3 H3N NH3
9.103
metal ionSquare planar: cis-trans 25.9
in a complex. isomerism
The structure of complex ions
Co SO42− Co Br−
metal ion and The two structures are isomers because they are non-superimposable.
ples of bidentate H3 N NH3 H3N NH3

ation in complexes DEFINITION
The terms cis and transNH are used in the same way as they areNH in
ne
H2 co-ordinate
and amino bond with organicthe central metal ion in 3a A polydentate ligand is3 one
chemistry.
e described as monodentate (or unidentate) because which forms two or more

’ with which to bind withTrans the central [Co(NH
cation. (The )5Br]SO4 [Co(NH )5SOcentral
4]Br
implies ‘opposite’ – notice thatco-ordinate
3 the ammoniabonds with3are
molecules the
‘tooth’.) arranged opposite each other metal
in thatinvolves
version, ionand in a complex.
so areinthe
H Figure 3.3.5 Ionization isomerism complex compounds whichchloride
the elements are the
O
form more than one bond ions.
a metal
with iontheand
− −
same but identity

O of the cation anion pair varies.
C − C = (or multidentate). Examples–of bidentate
−ydentate
=
− O −
o-ordinate
N
Obonds
H with theCis implies
central ‘on
O=the
cation in same C−
complexes side’ – in this instance that just means that the
−1,2-diaminoethane, ammonia molecules CH2
H2NCH2CH2NH–2 and C amino chloride
and the ions are next to each other.
O − − CH2 −
−
H
−
re 25.13).
glycine
Stereoisomerism N (geometric isomerism)
2+
Cu
Geometric isomerism CH2 occurs in complexes with square planar or octahedral
−
–
O−
geometry.
H ForCH a−complex with two ligands of one type and two of another type
C− NO − plane, 2
− −
inCHthe2 −square there are two different arrangements O possible of these

C−C =
H −ligands
−
H2NCH2CH2NH2
=
– geometric isomer, known as the
=
around the central ion. In the first
O – OCH O−
−
cis O
isomer, H 2 like ligands are in adjacent
the O= positions.C − In the second geometric
−
− N C
−
CH2
isomer, H the trans isomer, the like ligands – C −diagonally
isomersO − are CH2 − opposite each other.
−
9.104 H Properties of cis-trans
=
−
1,2-diaminoethane Biological
glycine O systems are often sensitive to the differenceNbetween geometric
2+
isomers. A well-known example of this Cu
is the geometric
isomer cisplatin, a
−
Fig A pair The
25.14 of geometrical isomers
complex ion formed bywill
EDTAhave different
–
O− chemical properties. CH 2not work in the same
2+ chemotherapy
with a Cu ion. EDTA binds cations so drug. Its trans isomer, transplatin, −
does
N − CH2
For example,
strongly way
that it can be at
usedall.sparingly
cisplatin is one of as the
an most successful C − CH anti-cancer
− drugs
O poisoning by trapping Pb2+
−
2
=
antidote
whilstto
= lead
the trans-isomer has no therapeutic effect.
CH2 CH −
2 ItCis also–used as a means of extending
ions. O – CH 2
O
−
−
, are particularly the shelf lifeOof manufactured foods, such as
−
−
central NCHmetal2CH2N salad dressings, by trapping metal ions which C H2O H2O
O the oxidation of vegetable
=
−
−
would catalyse NH oils H O Cl H2O Cl

CH2 − C =
t it makes them Cl 3 H3N ClO 2
CH 2 −–
O Pt2+ Pt2+ Cr3+ Cr3+
Fig 25.14 The complex ion formed by EDTA
EDTA
nd cations are with a Cu2+ ion. EDTA binds cations so
DEFINITION Cl NH3 Cl that it can be used
strongly NH3sparingly H
as2Oan Cl Cl OH2
ds and thethe
s from hexadentate
Greek ligand EDTA
A chelate is a complex ion in antidote to lead poisoning by trapping Pb2+
cisplatin transplatin H2O
nd forms a ions. It is also used as a means of extending H2O
which each ligand
TA (ethanediaminetetraethanoate), forms two or the shelf life of manufactured foods, such as
are particularly
orm six co-ordinate bonds more co-ordinate
with metalwith the salad dressings, by trapping metal ions which cis
the centralbonds trans
ple monodentate central metal ion.
inds so strongly with metal ions that it makes them would catalyse the oxidation of vegetable oils
tion as the
e 25.14). Figure 3.3.6 Geometric isomerism can be seen in square planar and octahedral complexes.
metal ion more
orm
holdbetween polydentate ligands and cations are
the metal DEFINITION
A
ounced ‘keelates’). This name comes from the Greek Trans-form
A chelate is a complex ion in
’s claw’. In these complexes theBligand
9.105 Octahedral:
forms cis-trans
a A ligands
B opposite
on
isomerism
sides which each ligand forms two or
e central metal ion. M of M, at 180° more co-ordinate
BOctahedral complexes of the type MA2B4 also exhibit cis–trans bonds with theFOR USE WITH THE IB DIPLOMA PROGRAM
CHEMISTRY:
gands are more powerful than simpleB monodentate central metal ion.
dcomplex
the positions isomerism.
ion is enhanced by chelation

A as the
in four
ntate ligand can hold the central metal ion more
compounds
he with the others still hold the A
bonds is broken, metal A
Cis-form Trans-form
tituent atoms B
A ligands on A B A ligands on
same side of B opposite sides
M M
M, at 90° of M, at 180°
–trans
nd isomerism of complex ions B
(geometric) B
examples of B B
nsional
t( shape of complex ions and the positions
III) chloride,
B A
ntral metal ion,
ifferent-coloured isomers can occur in four
Fig 25.15 Isomers of complexes of the type
ordinated complexes. MA
Isomers are compounds with A
n. 2B4
Cis-form
fferent arrangements of their constituent atoms B
A ligands on A
473same side of
M
M, at 90°
he type MA2B4 exhibit a kind of cis–trans (geometric) B
gure 25.15. One of the most striking examples of B
Bilal Hameed B Transition Elements
urs with tetraamminedichlorocobalt(
Bilal Hameed III) chloride, Marginalizer
wo isomers with this formula have different-coloured Fig 25.15 Isomers of complexes of the type
ue-violet, but the trans-form is green. MA2B4
ms in thisM topic have thin red construction lines to help you to
with the same molecular formula but with different arrangements
e the shapes. These are not bonds. Another way to represent
of their atoms in space. Transition metal complexes can form both
to uselinear
wedge bonds and dotted bonds. Wedge bonds come out
our
apermain
and shapes of bonds geometrical
dotted
isomers (cis-trans, or E-Z isomers)
go in (Figure 8). 40
3 and optical isomers.
15
omplexes using wedge 82 (a) (i) 36
Geometrical
rism in transition metal complexes isomerism
Here ligands differ inthe their
cobalt position Co in space relative to one another.
areatom, 1s22s22p .........................................
6
ve met isomerism in organic chemistry. Isomers compounds
This type of isomerism occurs in octahedral and
e same molecular formula but with differentthearrangements cobalt(II) ion, Co2+ 1s22s22p6 ......................................... +
square planar complexes. Take the octahedral OH2 [1]
atoms in space. Transition metal complexes 9. 106 can form
Octahedral: +
both cis-trans
− isomerism H 2 O of [CrCl OH2 2 2O)4]+
(H
sitions complex ion [CrCl
in an (cis-trans, or 2(H 2O) 4] isomers.
. The Cl ligands
rical isomers E-Z isomers) (ii)and
State optical
the colours you would observe when concentrated HCl (aq) is added to an aqueous
Cr
mplex are equivalent may be next to each other (the
Take the octahedral complex
solution of cobalt( II cis-
) or Z-
nitrate, ion
Co(NO form)
[CrCl
3)2. 2(H2O)4]+. The Cl— ligands may be
Give the formulae and geometry of the complexes formed.
etrical
ositions isomerism
in the other
or on oppositenext sides to ofeach theother central chromium
(the cis-form) or on opposite Cl sides of theClcentral
OH2
ion (the trans- or
chromium
E-form)
ands differ in their position in space relative to one another. ion (Figure
(the 9).
trans-form).
.............................................................................................................................................
es.

e of isomerism occurs in octahedral and .............................................................................................................................................

In the square planar complex OH2
platin, the+ OH2 +
planar complexes. Take the octahedral
− ligands
+ Cl may be next
H2O to each otherOH2 (the cis- Cl OH
.............................................................................................................................................
2
xnkion [CrCl2(H2O)4] . The Cl− ligands
or Z- form) or on opposite sides
Cr of the central Cr
next to each other (the cis- or Z- form) .............................................................................................................................................
ore about cisplatin chromium ion (the trans- or E-form). A pair of 6 H O Cl
pposite sides of the central chromium Cl Cl 2
....................................................................................................................................... [5]
hetrans-
actionorofE-form)
anti- (Figuregeometrical isomers
9).
will have OHdifferent
properties. For example, cisplatin is one of the
2 chemical
Isomers OH2
1(b) There are two theisomers

cis-form with the formula Ni(R3P)▲ Figure
2I2, but theonly 9 oneThestructure
trans-form cis- or with the formula
quare planar complex platin,most successful
the anti-cancer
Co(R 3P)2I2. (R = alkyl,
drugs whilst+ the ligand)
OH2R3P is a monodentate Z-isomer (top) and the
nds may be next to eachtrans-isomer
other (the cis-has no therapeuticCl effect,OH2
Draw diagrams showing the structure13 of Co(R3P)trans- or E-isomer (bottom)
2I2 and the two isomers of Ni(R3P)2I2.
m) or on opposite sides of the central Cr 23
um ion (the trans- or E-form). A pair ofdiagramH shows
(c) The the visible spectrum of a solution of [V(H2O)6]3+.
2O Cl
rical isomers will have different chemical OH2
es. For example, cisplatin is one of the ▲ Figure 9 The cis- or
ccessful anti-cancer drugs whilst the 9.107 Octahedral: cis-trans isomerism of [Co(NH3)4Cl2]+
Z-isomer (top) and the
mer has no therapeutic effect, trans- or E-isomer (bottom)
The left-hand isomer is the cis isomer as the two Cl ligands are beside−
each other,absorption
i.e. at 90° to each other. The right-hand isomer is the trans
isomer as the two Cl− ligands are opposite each other, i.e. at 180° to
each other.
Ni(R3P)2I2 Ni(R3P)2I2
blue+ green red +

Cl Cl
H3N 350Cl400 450 500 550 600
H3650
N 700 NH3
Co wavelength / nm Co
H3N NH3 H3N NH3
NH3the solution is.
State and explain what colour Cl
the cis-form
colour of solution ....................................................... the trans-form
cis isomer trans isomer
explanation ................................................................................................................................
Figure 25.21 Co(R3P)2I2
.............................................................................................................................................. [2]
[3]

Optical isomerism in octahedral complexes

[S'16 P41 Q02]
(d) 2(i) [Total: 9]
O)6]3+ reacts to form a mixture of isomeric octahedral
complexes.Optical isomers are non-superimposable and their optical activity allow
2
9.108 Skillthem check

to rotate the9701/41/M/J/16
plane of plane polarised light.[Turn One
overisomer rotates th
TIP [V(H O) ] + 2Cl [V(H O) Cl ] + 2H O
© UCLES 2016 3+ – +
2 6 2 4 2 2
plane to the left and is referred to as an l-isomer and one rotates the pl
You would not be expected to Complete the three-dimensional diagrams to show the two isomers of [V(H O) Cl ] .
to the right and is call the d-isomer. The ‘l’ is from laevorotatory (rotate 2 4 2
+
be able to distinguish between

the left) and ‘d’ is from dextrorotatory (rotates to the right).
the d and l forms basedBilal
onHameed
a Transition Elements WS 1
diagram. This would be carried Octahedral complexes formed with a bidentate ligand form two optica
out practically by determining the isomers. It is the connection ofVthe ligands by coordinate bonds within
V
effect of each on plane polarised octahedral shape which gives the different isomers.
light.
A racemic mixture of both isomers shows no overall rotation as there w
beisomer
equal1 isomer 2
concentrations of both and the overall rotations
[2]
would cancel
H2N
3+ 3+ other out.
H2N(ii) State the type of isomerism shown by isomer 1 and isomer 2 in (i).
H2N NH2 H2N NH2
Co
Figure 25.22 shows the two optical isomers formed when 1,2-diaminoe
Co ....................................................................................................................................... [1]
H2N NH2 H2N NH2 forms a complex with Co3+ ions. The ligands are represented by H2N—
H2Transition
N Elements H2N NH2. The two optical isomers have a differentBilal three-dimensional
Hameed spatia
arrangement of the ligands around the central metal ion.
Figure 25.22 Transition Elements WS 2 Bilal Hameed
41
37
9.109 Optical isomerism

In transition metal complexes optical isomerism occurs when there are
two or more bidentate ligands in an octahedral complex.
The two
and same structuralThe
isomers are
Stereoisomerism
transition
formula, but have ametals
fallsnon-superimposable
different arrangement in space.
into one of two categories: mirror images of each other.
23
● cis–trans (E/Z) isomerism
optical isomerism. + +

●
en en
-superimposable mirror images ofCis–trans
each Cl Cl
(E/Z) isomerism
plexes this occurs when there areThe
two or planar structure
square Cr of [Ni(NH ) Cl ] and the Cr
octahedral structure of
3 2 2
mplex (Figure 10). [Co(NH3)4Cl2] + give rise to cis–trans (E/Z) isomerism (Figure 6.14).
Cl Cl
en en
rotating one of the complexes around M M
Diamminedichloronickel(II) mirror
Tetraamminedichlorocobalt(III)
orine atoms are in the same position as – –
e able to see that the positions of the en en Cl
is an abbreviation for Cl
ethane-1,2-diamine:
est way to beCl–sure about this is to Cl–use H 3N and same structural formula, but have a different arrangement in space.
H3N
NH3 NH3 Stereoisomerism
NH3 falls into one of twoNHcategories:
3
Ni2+ Ni2+ Co3H
+
2C CH2 Co3+
Cl– H3 N
cis–trans (E/Z) isomerism
●
H3N H3N
chiral. They have identical chemical
–
Cl Figure 6.16 Optical isomers Cl–
NH3 H2N ofNH
a complex NH formed by three molecules
● 3 optical isomerism.
2
of a bidentate ligand.
ished by their effect on polarised light. Cl– NH3
ne of polarisation
Z-isomer of polarised lightE-isomer An example of a complexE-isomer Cis–trans (E/Z)isomers
ion with optical isomerism
Z-isomer is [Ni(H2NCH2CH2NH2)3]2+,
Optical Figure 10
▲isomerism Transition
of metalplanar
[Ni(H complexes
ockwise.
(cis-isomer)
9.110(trans-isomer)
shown in The
(trans-isomer)
Figure 6.17 square 2NCH
structure 2CH
(cis-isomer)of
2NH
[Ni(NH3 2 22)3]
) Cl ] and2+
the octahedral structure of
that are non-identical mirror
[Co(NH ) Climages of to cis–trans (E/Z) isomerism (Figure 6.14).
] give rise
+
Figure 6.14 Cis–trans (E/Z) isomers of diamminedichloronickel(II) and tetraamminedichlorocobalt(III
3 ).
4 2
each other (top) and the structure of the

In Figure 6.14, consider the bond angle between the two chloride ligands
ethane-1,2-diamine
Diamminedichloronickel(II) (en) ligand (bottom)
and the central metal ion.
Tetraamminedichlorocobalt(III)
m If the Cl−–(metalenion)–Cl− bond angle is 90°, a cisen (or Z) isomer forms.

Cl– Cl–
Synoptic link
●
m found in transition metal chemistry. ● If the ClCl−– –(metal ion)–ClNH− bond angle
Cl–
is 180°, a trans
HN
NH (or E) isomer 3 3
3 The ligand
NH3
H3N
NH3
H2NCH2CH2NH2
ula CrCl3 (H2O)6. Both chloride ions, Cl−, Cl– results. Ni See Topic 25.2, Optical
+ Ni + isomerism, Co + 2 2 3
is represented
Co3+
en 2+ H N H N 2+ HN
ligands. This compound can exist as three Ni for more detail aboutCloptical
NH
– Ni NH
3 3
as 3
en
Cl–
Optical isomerism 3 3
en
how many of the chloride ions are bound to

Octahedral complexes isomerism
can also in organic
form optical chemistry.
isomers which are Cl –
NH3
and how many are free as negative ions.non-superimposable
Z-isomer
en mirror images of each other.
E-isomer
enOptical isomerismE-isomer
en can Z-isomer
only occur(cis-isomer)
with a multi-dentate ligand (trans-isomer) (trans-isomer)
for example 1,2-diaminoethane, (cis-isomer)
2
NCH6.14
HFigure 2
CHCis–trans
2
NH2. Each
Summary questions
(E/Z)of the NH
isomers
they can approach the central imaginary
2
groups has a lone IIpair
of diamminedichloronickel( ) andof electrons and
tetraamminedichlorocobalt(
metal ion in a vertical plane or a horizontal
III).
l− violet plane (Figure 6.15). mirror In Figure 6.14, consider the bond angle between the two chloride ligands
Figure 6.17 Optical isomers of1[Ni(H
a2NCH
Predict
2
)and
CH2NHthe
2 3
the central metal ion.
]2+. shapes of the
2Cl− + H2O light green ● If theThis Cl
ligand
− is in the
–(metal ion)–Cl− bond angle is 90°, a cis (or Z) isomer forms.
following: horizontal plane.
These two ligands If the2+Cl –(metal
it is ion)–Cl bond angleofis the
180°, a trans (or E) isomer
− −
Cl− + 2H2O As is the case with
i organic
● molecules, the asymmetry
dark green are in the vertical [Cu(H2O) ]
results.
6isomerism
structure
plane, but twisted at that leads to optical as the two molecules cannot be
2+
ii Mare
[Cu(NH 3)6]spatially not the same.
90º to each superimposed
other. and therefore
d H2O allows them to act as ligands? Optical isomerism
iii various 2−
[CuClOctahedral
same concentration of each compound, Complex ions have 4]uses. A particularly
complexes can interesting example
also form optical is which are
isomers
conduct electricity best? Explain your answer. the cis (Z) form b What of theismolecule
the [PtCl2(NH3)mirror
co-ordination
non-superimposable
only occur
2
]. (The platinum
images is other.
of each present Optical isomerism can
as platinum(II), so the complex has with a multi-dentate
no overall charge.)ligand for exampleof1,2-diaminoethane,
The structure
d not those bonded as
Cl NHligands) will react
Figure 6.15 The shape of a number ofH2the
complex ion showing M transition
surrounded by
3
9. 111threeOptical
molecules a isomerism
[PtClof2(NH ) ] is shown
bidentate
3 2 inNCHcomplex
ligand. in Figure 6.18.
2
ions
CH2NH2. Each of the NH2 groups has a lone pair of electrons and
balanced equation Pt
for the reaction of metal in each they cancomplex
approachinthea?central metal ion in a vertical plane or a horizontal
Cl NH This compound is known as cis-platin.
plane (Figure Used
6.15). during chemotherapy as an
rate solution. 3
Optical a
anti-cancer cdrug,Explain
This gives rise to two possible
isomers of complex it isomerswhy
isformed the
(Figure
by
a colourless co-
6.16).
three
liquid molecules
that of a bidentate
is usually administered by a
Figure 6.18 Cis-platin.
act with most silver nitrate? Explain
ligand:your drip into a vein. ordination
It works by numbers
binding onto arethe DNA of cancerousThis ligand
cells is in the
and
horizontal plane.
preventing their division. These two ligands
different.are in the vertical
somerism is shown by Compound 3. The importance of the exact shape

plane, but twistedand
at structure of the molecule
26 2 Benzene-1,2-dicarboxylate
90º to each other. is M
ompound 1 is: is emphasised by the fact that the trans isomer is ineffective. Great
+ care has to shown
be taken below.
when using chemotherapy to treat patients as
O
the compounds can lead to unpleasant side effects and a balance
—
—
has to be struck between the advantages

– of the treatment and the
M Figure C —The
6.15 O shape of a complex M ion showing M surrounded by
disadvantages. three—
molecules of a bidentate ligand.
+ 3Cl–
This—
gives rise to two possible isomers (Figure 6.16).
–
C—O
—
—
O 127
126 a Suggest which atoms are Figure 6.16 Optical isomers of a complex formed by three molecules of a bidentate ligand.
a of Compound 2 in the same style.
likely to form co-ordinate
bonds
An example of a complex with
ion with a metal
optical ion.is [Ni(H2NCH2CH2NH2)3]2+,
isomers
shown in Figure 6.17
b Mark the lone pairs.
c Is it likely to be a mono-,
Bilal Hameed bi-, or hexadentate ligand? Marginalizer
en
en
The ligand
371 H2NCH2CH2NH2
is represented
42
38
9.112 Optical isomerism in complex ions

+
Optical isomers are said to be chiral.
Cl
H3N Cl H3N
They have identical chemical properties but can be distinguished by Co
their effect on polarised light.
H3N NH3 H3N
NH3
One isomer will rotate the plane of polarisation of polarisedTransition
light
Chapter 24:Chapter 24:elements
Transition elements
clockwise and the other anticlockwise.
cis isomer
Figure 25.21
no double bond noexists.
doubleInbond
this exists.
case, the
In term geometric
this case, the term geometric
QUESTION QUESTION
isomerism refers to complexes
isomerism refers with the samewith
to complexes molecular
the same molecular
4 a What is the
4 oxidation
a What isnumber of the transition
the oxidation formula but different
number of the transition formulageometrical
but differentarrangements of their
geometrical arrangements of their Optical isomerism in octah
metal in each ofmetal
the following
in each of the following complexes? atoms. Examples
complexes? atoms. cis- and trans-platin
are Examples are cis- and(Figure 24.8). (Figure 24.8).
trans-platin
i [Co(NH3)6]3+i [Co(NH3)6]3+ In cis-platin, the chlorine atoms
In cis-platin, are nextatoms
the chlorine to each
areother
next to each other Optical isomers are non-superim
in the square complex trans-platin,
but incomplex but inthey are
ii [Ni(CN)4]2– ii [Ni(CN)4]2– in the square trans-platin, they are them to rotate the plane of plan
iii [Cr(OH)6]3– iii [Cr(OH)6]3–
3+
TIP opposite. The opposite.
propertiesThe
are slightly different.
of these geometrical
properties
are slightly different.
of theseisomers
geometrical isomers
plane to the left and is referred
iv [Co(en)3]
You would not be expected toNHCI3
iv [Co(en)3]3+
v Cu(OH)2(H2O)
v 4 Cu(OH)2(H2O)4 CI Cl 3 3 3 NH to the
NHCl right NH
and is call the d-iso
b EDTA4– ionsbcanEDTA
act as
4– ligands. A single EDTA 4–
ions can act as ligands. A single EDTA 4– Pt Pt the left) and ‘d’ is from dextroro
Pt Pt
ion can form sixion
co-ordinate
can form six the
bonds to d andbondsl to
a central
co-ordinate forms
a central based on a
CI CINH3 H3N NH3 H3NCl Cl
transition metaltransition
ion to form an octahedral
metal ion to form an octahedral
complex.9.It 113
is called aOptical
complex.hexadentate diagram.
It is calledligand. Give theligand.would
a isomerism
hexadentate This Give be cis-platin
inthecomplex carried ions Octahedral
cis-platin trans-platin trans-platin complexes formed w
formula of suchformula
a complex
and EDTA4–. and EDTA4–.
out
formed
of such practically
between
a complex formed by
Ni2+ between Ni2+
determining
Figure 24.8 The 24.8 the
geometrical
Figure Theisomers, isomers.
cis-platin
geometrical It isandthe connection of
and cis-platin
isomers,
Here are the two optical
effect of isomers
each formed
on plane when
trans-platin. 1,2-diaminoethane
polarised
trans-platin.
haveoctahedral shape which gives th
c Which ligands
INORGANIC CHEMISTRY c inWhich
Tableligands
24.4 areinbidentate?
Table 24.4 are bidentate?
forms a complex with Co3+ ions. The twohas optical isomers adrug.
light. Cis-platin been used
Cis-platin as an
has anti-cancer
been used as an It acts bydrug. It acts by
anti-cancer
different three-dimensional spatialbinding
arrangement
to sections
bindingofthe
of tothe
DNAligands
inofcancer
sections around
the Acells,inpreventing
DNAracemiccancer cells, preventing of
mixture both isom
the central metal ion. cell division. cell division.
Stereoisomerism in transition
Stereoisomerism metal Number
in transition
Table 24.5 The properties of the three isomers metal
of free Number of free Stereoisomerism is commonly shown
Stereoisomerism is commonlyby octahedral
shown by octahedral be equal concentrations of both
of CrCl3.6H2O
complexescomplexes Colour Cl − ions H2O molecules
(six co-ordinate) (sixcomplexes
Structure
associated
co-ordinate) complexes with bidentatewith bidentate
associated
In Chapter 14 In (pages 195–6)
Chapter
purple
we learnt
14 (pages about
195–6) Htwo
we 2learnt
3 3+ 0
N about two ligands. An example H2NisAn
ligands.
[Cr(H2O)63+
theexample
3+
]3Cl −
complexiscontaining
the complex containing
other out.
blue-green 2 [Cr(H2O)5Cl ]2+2Cl −.H2O
types of stereoisomerism: geometric
types of stereoisomerism: isomerism
H geometric
N andisomerism
NH nickel as1the
and H transition
N metal
nickel as the and 1,2-diaminoethane
transition
NH metal and 1,2-diaminoethane
2 2 2 2
optical isomerism. The
optical presence of
isomerism.
green
a double
The presencebond
of ain
Co
1
double bond(NH
2
in 2CH2CH2(NH NH22)CH [Cr(H2O)4Clligand
as the bidentate
+ −
Figure 25.22 shows the373
2] Cl .2H 2O
(Figure
Co2CH2NH2) as the bidentate ligand (Figure
two opt
373
1,2-dibromoethane means that two geometrical
that twoisomers 24.9). The two24.9).
isomers
Theare stereoisomers because the two
1,2-dibromoethane
(cis-trans isomers) are possible.
(cis-trans
means
H2N isomerism
Complexes
isomers)Geometric
are possible.can
geometrical isomers
Geometric NHisomerism
also show 2stereochemistry. HA2N good
different molecules are
different
two
example NH
mirrorofimages
molecules this
2 areis mirror
the forms a complex with Co3+ ions
isomers are stereoisomers
complex
of each other and
images
because the two
of each other and
is also possibleisin transition
also possiblemetal
in transition 2H
ioncomplexes,
[Ni(en)metal
(NH )2]2+, where where
N3complexes,
2where
‘en’cannot H2Nbe superimposed.
is usedbeassuperimposed.
an abbreviation
cannot NH . The two optical isomers h
for 1,2-diaminoethane,
NH CH CH NH . This complex can exist in cis and trans forms. The cis form (but 2
2 2 2 2
not the trans) has a chiral centre (the nickel atom) and can be resolved arrangement
into optical of the ligands arou
a Figure
isomers a
CH(see
25.22
Figure 24.12).2+
2 CH2
2+
CH2
2+
CH2
2+
Figure 24.12 The stereochemistry of H2C NH2 H C NH2 H2N CH2 H2N CH2
2 H 2C CH2
[Ni(en)2(NH3)2]2+ NH2 H N CH2
H2N NH
H2N
2 NH2 H C
H22N NH
H2N2 NH22
TEST YOURSELF 3
Br CH2 HCH
2C 2 HC
H2C H2Ni
N Ni 2
NH CH2 H 2N Ni 2 Ni Br NH
Br 2
CH2 2C 2
HCH H2C
H2N
+
NNH2
H2Co NH2 H2N 1 For the following complexe
+
H2NNH2
Co
+
Co2
NH
H 2C
ANH[CuCl 4]2−
CH2
H2C H2NH
N 2H2C NH22
NH H2N CH2BrH2N Br CH2
H N 2
CH CH 2
9.114 Optical isomerism in complex Br CH 2
H C
2
NH
ions H N BCH[NiEDTA]2−
2 CH2
2
2 2 2
C [Ag(NH3)2]+
H C CH 2 2
b b 2+ 2+ 2+ 2+
en
trans form en en cis form
en
2+
D [Co(H2O)6]3+
Ni also forms Ni en with
a complex en en
Ni three 1,2-diaminoethane
Ni en Ni ligands. This has only the cis
form as the distance is too large for the ligand to stretch across the trans positions. E [Co(H2NCH2CH2NH2)3]2+
The cis formen can also be resolved
en
into optical
en isomers (seeenFigure 24.13).
F [Pt(NH3)2Cl 2]
Figure 24.13 Optical isomerism
Figure 24.9 The
[Ni(NH CH CH NH ) ] ion 2+
in
Figure the
two non-superimposable
24.9 The two 24_12 optical
H C isomers
non-superimposable
Cam/Chem AS&A2 of Ni(NH
optical CH CHofNH
isomers 2
) :CH
Ni(NH a the
CH full ) CH : a thebfull
NH structure;
2 2
a)structure
a simplified
structure;
2 b aState
simplifiedthe
2+
2 3 2 2
shape of all the
structure
2 2 3
2+
2
NH H N
with ‘en’ representing
with ‘en’a representing
molecule of 1,2-diaminoethane.
b)
2 2 2 23 CH
aHmolecule
C of 1,2-diaminoethane.
State the coordination n
2 2
2 2
Barking Dog Art
H N NH 2 CH H C H N 2
NH
2 c) State the oxidation state
2 2
2
complexes.
Ni Ni
CH2 H2C
NH2 H 2N
H2N NH2
d) Which one of the comple
H 2C
H2C
NH2 H 2N
CH2
CH2
e) Which one of the comple
522
Transition Elements
Cis- and trans-platin
An important example of cis/trans isomerism is the drug cisplatin. This has a Pt atom
joined to two chlorine atoms and two ammonia molecules. It is a square planar
complex and can, therefore, exist in both cis and trans forms. Bilal
● Formation
Hameed of colo
Marginalizer24_13 Cam/Chem AS&A2 Bilal Hameed
Cl Cl
Transition metal ions show dist
Barking Dog Art
Cl Pt NH3 NH3 Pt NH3
identification. The main colour
Optical isomerism in octahedral compl
Optical isomers are non-superimposable and
43 them to rotate the plane of plane polarised lig
TIP 39
plane to the left and is referred to as an l-isom
You would not be expected to to the right and is call the d-isomer. The ‘l’ is
the left) and ‘d’ is from dextrorotatory (rotate
the d and l forms based on a
9.115 Optical diagram. This would
isomerism be carried
in complex ions Octahedral complexes formed with a bidenta
out practically by determining the isomers. It is the connection of the ligands by
Here are the two optical
effect ofisomers
each formed
on when
plane 1,2-diaminoethane
polarised
forms a complex with Co3+ ions. The two optical isomers haveoctahedral
a shape which gives the different iso
light.
different three-dimensional spatial arrangement of the ligands A
around
racemic mixture of both isomers shows no
the central metal ion.
be equal concentrations of both and the over
H2N
3+
H2N
3+ other out.
H2N NH2 H2N NH2
Co Co
Figure 25.22 shows the two optical isomers fo
H2N NH2 H2N NH2 forms a complex with Co3+ ions. The ligands
H2N H2N NH2. The two optical isomers have a different
arrangement of the ligands around the central
Figure 25.22
TEST YOURSELF 3
1 For the following complexes:
A [CuCl 4]2−
9.116 Optical isomerism in cis-[Co(en)2Br2] +
B [NiEDTA]2−
transition metals Optical isomers of a complex formed by two molecules of a bidentate C [Ag(NH3)2]+
ligand and two ions of a monodentate ligand, e.g. cis-[Co(en)2Br2]+
D [Co(H2 O)6]3+
13.1 First-row d-block elements 467
omplexes containing chelating agents are usually much more stable than those formed E [Co(H2NCH2CH2NH2)3]2+
Optical isomerism
monodentate ligands. This is termed the chelate effect,CH
and is due to an increase in
Octahedral
py. isomers containing a bidentate
For example:
2
CH
F [Pt(NH3)2Cl 2]
2
HC NH HN CH
ligand can form a pair of complexes that are
2 2
a) State the shape of all the complexes.
2 2
Ni(H 2+ 2+ K = 4.0 × 108

2O)images
mirror 6] (aq) of
+ each
6NH3other
(aq) ! [Ni(NH
(Figure 3)6] (aq)H+N6H2O(l)
13.24). Br Br NH b) State the coordination number of all th
2
Ni(H
These 2+
2O)molecules
6] (aq) +are3en(aq)
known!as[Ni(en) 3+
3] (aq) + 6H2O(l)
enantiomers. K = 2.0 × 1018 13.2 Coloured complexes 471
2
This form of isomerism is called optical

Co+ Co+ c) State the oxidation state of the transiti
e en represents the bidentate ligand, 1,2-diaminoethane, H2N–(CH2Br )2–NH2Br .
H2N NH2 complexes.
isomerism (Chapter 20) because the two
forms will rotate plane-polarized
Finding the formula of a complexisolated light in
13.2 Coloured complexes
ion atom, but split into two sub-levelsCHin a complexd)
– d-orbitals have the same energy in an
equal but opposite directions. H2C NH2 H2N ion;Which onefield
the electric of the complexes would exh
of ligands
CHto split so thate)
2
lorimeter can be used to measure the concentrations may cause of chemicals that are themselves
CH2the d-orbitals in complex ions theWhich
energy of one
an of the complexes would exh
electron
red or
■ which produce
Valence bond a coloured substance during
(VB) theory a chemical
transition reaction
between (Chapter
them 6). By to a2 photon of visible light
corresponds
wing the changes in absorbance that take place in ■ reactions involving the formation of
522 Figure 13.24 The enantiomers of cis-[Co(en) 2Br2] ,
+
●
red complexinions,
Bonding a colorimeter
complex ions can be used to ■ determine the formulas of these complex
Figure 13.33 isshows
where The colours
en represents of complex ions
1,2-diaminoethane
addedthe
to results of measuring the absorbance of a) series of mixtures of
If ammonia a solution containing
Formation of coloured ion
(H2NCH2CH2NH
mol −3
dm copper(ii) 2+ White light can 2 result from the combination of only red, green and blue light. When equal
(aq), andis0.01 mol dm EDTA (aq). EDTA4− is a hexadentate
−3 4−
chromium(iii) ions,ions, Cu complex
a purple brightnesses of these are combined and projected on a screen, white light is produced (Figure 13.35).
dformed.
and forms very stable
The chromium(iii) complex ionsa with d-block
d3green metal ions.
redion yellow
has configuration
The screen and so has three
appears yellowunpaired
when redelectrons.
and greenThis light aloneTransition
overlap. The combination of red and blue
leaves two empty d-orbitals as well as one 4s and metal ions show distinct colours th
light produces the bluish-red colour oflone
three 4p orbitals that can receive pairs Green and
magenta. blue produce the greenish-blue colour
9. 117
white Optical
from the ammonia molecules to form the hexaamminechromium(iii) isomerism
called cyan. Almost anycomplex
in cis-octahedral
O can
colour ion,be[Cr(NH
made by
3+ complexes
3)6overlapping
] identification. Theandmain
light of three colours colours
adjusting the of the some
as shown in Figure 13.25.magenta
The diagram cyanis appropriate for all octahedral chromium(iii) complexes
brightness of each – colour. Red, green and 2 –
blue light are known as primary colours since all other
because the 3d electrons alwaysWhat singlyisoccupy
blue
also interesting
different
colours can
to note
orbitals. O is that
be formed from them.
C in an octahedral molecule that
● Copper(II) compounds are mainly blue in
has two bidentateWhen ligands,
O white and two other
light is shoneCH similar
on ligands,
2a chemical can not
substance, onlyas a solid or in solution, some
C CH2 ●either
Iron(II) compounds are pale green in colou
3d exhibit
■ Figure 13.35 cis-trans
4s lightisomerism
is
–O 4p
absorbed but
and it’s
somecis-form
is
N can
reflected. also exhibit optical
● Cobalt(II) compounds are pink in colour.
Cr [Ar] Primary isomerism.
and
■ If all the light is absorbed then CH2the substance appears ‘black’.
secondary colours ■ If only certain wavelengths are absorbed then the compound will appear
Cr [Ar]
The trans molecule of such Cu
2+
an ion, however, will not exhibit optical In solution thesecoloured.
ions become hexaaqua catio
■ If all the light is reflected then CH the colour of the substance will appear ‘white’.
Cr(NH ) [Ar] isomerism. Cis 2
Most
– en d-block metal + compounds are coloured, both
en + in solution and in the solid state. The colours of
2 3 4 5 6 7 8 9 10 O (but notCl N
many all) of
Cmonodentate ligands
these
H2C compounds Cl are due to the presence of incompletely filled 3d sub-levels.
The
1 formation
2 3 of4 a chromium(iii)
5 6 7 complex
8 9 ion with In sixCo
an isolated gaseous d-block therefore
metal requires
Co
atom, the five 3d sub-levels all have different orientations
no electronic reorganization of the d electrons. in O
However, the situation
– isCmore CHcomplicated
2 if a
space (shapes), Cl O but identical energies.
Cl However, in a complex ion the 3d sub-levels are orientated
transition
9 8 metal
7 ion has
6 5 more 4 than
3 three2 3d
1 electrons,
en forrelative
differently example the ligands.
to the iron(iii)The ion,3dwhich has
en aclose to a ligand will experience repulsion and be
electrons
d5 configuration with half-filled 3d 469839_25_AQA_Chem_510-535.indd
orbitals (Figure 13.26). 522
O
raised in energy. The 3d electrons located further away from the ligand will be reduced in energy.
nce of ten mixtures of 0.01 mol dm−3 Cu2+(aq) The 3d13.34
■ Figure sub-level has now
Structure of the been ‘split’ion
complex into two energy levels. Octahedral complexes are very
3d 4s 4p
aq) common
formed betweenand the copper(
splittingII) of
ionstheandd sub-levels
EDTA4− ions is as shown in Figure 13.36 for the hydrated titanium(iii)
Fe [Ar] ion. Two d-orbitals are raised in energy; three d-orbitals are lowered in energy. (Different d–d splitting
peak
Fe of absorbance corresponds to mixing equalpatterns volumesare ofobserved
the two in tetrahedral,
solutions, which bothplanar and linear complexes. The terms t2g and eg are
square
[Ar] Bilal Hameed and are based on symmetry considerations.) Transition Elements
the same concentration. Hence, copper(ii) ionsused
Bilal Hameed and to EDTAdescribe the split
4− react in a 3d 1 : 1sub-levels
molar ratio Marginalizer
re 13.34). The formula ■of3d the complex 2−. 4p
Figure 13.36 is [Cu(EDTA)]
4s 4d
DTA
[Fe(H is
O) used
] [Ar]in chelation
Thetherapy,
splitting where
of the chelating agents are used to remove toxic heavy
ls,high
such as mercury, lead
spin 3dand uranium,
sub-levels in from the body. The ions of the heavy metals e
g 25.16 Yuvraj Singh is an Indian be used in chemotherapy for the treatment of certain cancers, but the
ternational cricketer and a cancer survivor. 11 Explain the following statements:
trans-isomer –has no effect.–Draw the structure of cis-platin and write its
ter several rounds of chemotherapy, he a Ethanedioate, OOC
correct chemical − COO , is a bidentate ligand.
name.
turned to cricket and was selected in India’s
ational team. b Aqueous copper(II) sulfate turns blue litmus red.
12 Write the following ions in44
order of increasing stability and explain your order:
40
[Cu(NH3)4(H2O)2]2+, [Cu(H2NCH2CH2NH2)3]2+, [Cu(EDTA)]2–
25.10 13 The neutral complex, PtCl2(NH3)2, in which Cl– ions and NH3 molecules
Ligand exchange reactions
act as ligands to the platinum ion, Pt2+, has two isomers.
a Explain why a square-planar structure can have isomers, but a
118 Ligand
9.tetrahedral exchange
structure cannot. reactions
In this section you will learn to: In bSection
AThe isomers
ligand 7.16 weofnoticed
exchange PtCl 2(NH 3)2is
that
reaction are calledreactions
acid–base
a reversible and trans-platin.
cis-reactioninvolve
in which ligandcan
Cis-platin
competitions
one
25.16 Yuvraj Singh is an Indian betweenbe used in chemotherapy
different bases for H + for the treatment of certain cancers, but the
ions. In a similar fashion, complexing reactions
•national
Give cricketer
examples andof wheresurvivor.
a cancer ligands tries to replace the existing ligand in a complex ion.
involvetrans-isomer
competitions has between
no effect.different
Draw the structure
ligands of cis-platin
for metal and results
ions. This write its in
are exchanged
several for other types
rounds of chemotherapy, he of
ned to cricket and was selected in India’s correct
reactions
For chemical
in which
example, when name.
metal ionshydroxide
sodium exchangesolution
one ligand for another.
is added to aqueous copper(II)
ligand
onal team.
• Write out balanced equations for For sulfate,
example, hydroxide ions displace
when sodium water solution
hydroxide moleculesisfrom hydrated
added copper(II)
to aqueous copper(II)
these reactions ions forming a pale blue precipitate of copper(II) hydroxide.
sulfate, hydroxide ions displace water molecules from hydrated copper( In effect, this isII)an
ions
uncharged
a paleinsoluble complex.of
copper(II) hydroxide. In effect, this is an
25.10
forming blue precipitate
uncharged insoluble complex.
Ligand exchange
[Cu(H 2+ reactions
–
2O)6] (aq) + 2OH (aq) → [Cu(H2O)4(OH)2](s) + 2H2O(l)
pale blue soln pale blue ppt
NOTE
this section you will learn to: In Section 7.16 we noticed that acid–base reactions involve competitions
Give examples of where ligands betweenreaction
The forming
different theHpale
bases for + blueInprecipitate
ions. of copper(
a similar fashion, II) hydroxide is
complexing reactions
usually simplified to:
involve competitions between different ligands for metal ions. This results in
are exchanged for other types of
ligand reactions in which
Cu2+(aq) + 2OHmetal
–
(aq) →ions exchange
Cu(OH)2(s) one ligand for another.
Write out balanced equations for For example, when sodium hydroxide solution is added to aqueous copper(II)
If excess ammonia solution is now added, the pale blue precipitate dissolves
these reactions sulfate, hydroxide ions displace water molecules from hydrated copper(II) ions
as water molecules and hydroxide ions around the Cu2+ ion are exchanged
forming a pale
9.119 Ligandblue precipitate of
exchange copper( II) hydroxide. In 2+ effect, this is an
for ammonia molecules. A deep bluereaction
solution of of Cu with
tetraamminecopper( NaOH II) ions is
uncharged insoluble complex.
produced:
[Cu(H2O)6]2+(aq) + 2OH–(aq) → [Cu(H2O)4(OH) 2](s) + 2H O(l)
[Cu(H2O)4(OH) 2](s) + 4NH3(aq) → [Cu(NH3)4pale (H2O)2]2+(aq) + 2OH–2(aq) + 2H2O(l)
pale blue soln blue ppt
pale blue ppte deep blue soln \
An exchange of ligands also occurs when concentrated hydrochloric acid reacts

NOTE The above reaction forming the pale blue precipitate of copper(ii)
withreaction
The copper(forming
II) sulfate solution. In this case, the colour changes from pale blue
the simplified
pale blue precipitate of copper(II) hydroxide is
hydroxide is usually to:
74 usually simplified to:

Cu2+(aq) + 2OH–(aq)Cu + 2OH
2+ — (aq) → Cu(OH)2 (s)
→(aq)Cu(OH)2(s)
If excess ammonia solution is now added, the pale blue precipitate dissolves
as water molecules and hydroxide ions around the Cu2+ ion are exchanged
for ammonia molecules. A deep blue solution of tetraamminecopper(II) ions is
produced:
[Cu(H2O)4(OH)2](s) + 4NH3(aq) → [Cu(NH3)4(H2O)2]2+(aq) + 2OH–(aq) + 2H2O(l)
pale blue ppte deep blue soln
An exchange of ligands also occurs when concentrated hydrochloric acid reacts
with copper(II) sulfate solution. In this case, the colour changes from pale blue
9.120 Cu2+ with NH3

When excess concentrated ammonia solution is added to pale blue
copper(II) sulfate solution, ammonia molecules are exchanged for water
molecules around the central Cu2+ ion and the colour changes to a
deep blue.  
[Cu(H2O)6]2+(aq) + 4NH3 (aq) ⇌ [Cu(NH3)4(H2O)2]2+ (aq) + 4H2O (l)

pale blue solution deep blue solution

19 Predict the likely shape of the following complex ions:
a) [Ag(CN)2]− b) [Fe(CN)6]3−
10 [NiCl4]2− d) [CrCl45
c) +
2(H2O)4]
41
Ligand exchange
20 Explain how the amino reactions
acid glycine (H NCH COOH) can act as a
2 2
bidentate ligand.
21 a) Why is EDTA4− described as a hexadentate ligand?
4−
u will learn to: In Sectionb)7.16
Whatweisnoticed
the overall
thatshape
acid–base EDTA complex
of thereactions involveincompetitions
Figure 15.17?
where ligands
9.
between 121 Cu
22 different
2+ with NH
a) Draw abases
diagram
for H + 3
to represent
ions. In athe complex
similar ion formed
fashion, between
complexing a
reactions
r other types of Cr3+ ion and
involve competitions three ethanedioate
between ions −for
different ligands metal2−ions.
O2C–CO . This results in
Thein
reactions reaction takes place in two stages.
b) which
What ismetal ions exchange
the overall onecomplex
shape of this ligand for
ion?another.
23 a) Predict an order of stability for the complex ions 2+,
ed equations for At first
For example, the alkaline
when solution
sodium of ammonia
hydroxide removes
solution is added to[Ni(NH
protons 3)6] copper(
from
aqueous the II)
[Ni(en) 2+
] and [Ni(EDTA)] 2− Figure 15.19 The blue pigment in this rare
sulfate, hydroxide
hydrated 3ions
copper(ii) displace
ions give a. molecules
to water from hydrated
pale blue precipitate of thecopper( II) ions
hydrated Mauritius two pence stamp from 1847 is
forming ab)
pale blue
Explain
hydroxide.
yourprecipitate of copper(II) hydroxide. In effect, this is an
prediction.
uncharged insoluble complex. called Prussian blue. Its correct chemical
24 Refer to Figure 15.19. Write the formula of: name is iron(iii) hexacyanoferrate(ii).
2+ –
[Cu(H 2O)hexacyanoferrate(ii)
a) the 6] (aq) + 2OH (aq) ion→ [Cu(H 2O)4hexacyanoferrate(ii).
b) iron(iii) (OH)2](s) + 2H2O(l)
pale blue soln pale blue ppt

NOTE 15.9 Ligand exchange reactions

TheComplex
reactionions
forming
oftenthe pale
react by blue precipitate
exchanging of copper(
one ligand II) hydroxide
for another. These isligand
usually simplified
exchange to: are often reversible and the changes of ligand are sometimes
reactions
Cuaccompanied
2+
(aq) + 2OH–by colour
(aq) → changes.
Cu(OH)2(s) For example, when excess concentrated
ammonia solution is added to pale blue copper(ii) sulfate solution, ammonia
molecules
If excess are exchanged
ammonia solution isfor water
now molecules
added, the palearound Cu2+ ion
the central dissolves
blue precipitate
and the colour changes to a deep ions
blue.around
The reaction 2+
takesion
place
as water molecules and hydroxide the Cu areinexchanged
two stages.
At first themolecules.
for ammonia alkaline solution
A deepofblue
ammonia removes
solution protons from the hydrated
of tetraamminecopper( II) ions is
copper(ii) ions to give a pale blue precipitate of the hydrated hydroxide.
produced:
O)122
[Cu(H9.
2[Cu(H Cu
4(OH)
2O)
2+
2](s)
2+ + with NH−→
4NH (aq) 3 [Cu(NH
6] (aq) + 32OH (aq) 3)42(H
! [Cu(H O)2O)
2+
2] (aq)
4(OH)
2OH–(aq) + 2H2O(l)
2](s) + 2H 2O(l)
pale blue
pale ppte
blue solution deep
paleblue
bluesoln
precipitate
Then
An exchange the ofligand
ligandsexchange
also takes
occurs place
when as the precipitate
concentrated redissolves reacts
hydrochloric to
Then the ligand exchange takes place as the precipitate redissolves acid
to give
give
withthe the
copper( deep
) sulfateblue solution.
solution. In this case, the colour changes from pale blue

deep IIblue solution.
[Cu(H2O)4(OH)2](s) + 4NH3(aq)
pale blue precipitate
! [Cu(NH3)4(H2O)2]2+(aq) + 2H2O(l) + 2OH−(aq)
deep blue solution
The ligands NH3 and H2O are both uncharged and similar in size. This
The ligands
allows exchangeNHreactions
3 and H2O are both
between uncharged
these ligands and similar
without in size.inThis
a change co-
allows exchange
ordination number ofreactions
the metalbetween
ion. these ligands without a change in
A co- ordination
ligand exchangenumber
reactionofalso
theoccurs
metal when
ion. concentrated hydrochloric acid
is added to copper(ii) sulfate solution. This time, the colour changes from
pale blue to yellow as Cl− ions replace water molecules around the Cu2+ ion. Tip
[Cu(H2O)6]2+(aq) + 4Cl−(aq) ! [CuCl4]2−(aq) + 6H2O(l) A solution of a copper(ii) salt may turn
pale blue yellow green and not yellow if the concentration
of added chloride ions is not high
In this case, however, the ligand exchange involves a change in co-ordination
enough to convert all the blue hydrated
number. Chloride ions are larger than water molecules, so fewer chloride
ions to the yellow chloro complex.
ions can fit round the central Cu2+ ion.
9.123 Cu with NH3
2+
15.9 Ligand exchange reactions 435

The overall change is a ligand exchange reaction and is a reversible
reaction.
[Cu(H2O)6]2+(aq) + 4NH3(aq) ⇌ [Cu(NH3)4(H2O)2]2+ (aq) + 4H2O(l)

469983_15_Chem_Y1-2_418-449.indd 435 13/04/19 10:03 PM
This is a reversible reaction and if the dark blue complex

[Cu(NH3)4(H2O)2]2+ is diluted, the pale blue colour of the [Cu(H2O)6]2+ ion
is restored.

Ligand-exchange reactions
b) What is the overall shape of this complex ion?
23 a) Predict an order of stability for the complex ions [Ni(NH3)6]2+, 2+
When ammonia is added to a solution containing aqueous Cu Figureions,
15.19four of pt
The blue
[Ni(en)3]2+ and [Ni(EDTA)]2−.
water molecules are substituted by ammonia, producing the Mauritius cuprammonium
two pence stai
b) Explain your46prediction.
This is an example of 42a ligand-exchange reaction, the substitution called Prussian
of blue.
one Its
li
24 Refer to Figure 15.19. Write the formula of: name is iron(iii) hexacya
by another:
a) the hexacyanoferrate(ii) ion b) iron(iii) hexacyanoferrate(ii).
Cu(H2O)62+(aq) + 4NH3(aq) → [Cu(NH3)4(H2O)2]2+(aq) + 4H2O(l)
9.12415.9With
Ligand
NH3 exchange reactions
Cu2+
This is a reversible reaction and if the purple complex [Cu(NH3)4(H2O)2]2+(aq)]
Complex
There ions often
is competition react by
between theexchanging
H 2O and NHone ligand for to
another. These ligand
is diluted, the pale blue colour3 molecules
of the [Cu(H attach 2+
2O)6] (aq)] ion is restored. There is
exchange
themselves toreactions are ion.
the copper often

reversible and the changes of ligand are sometimes
competition
accompanied by colourbetween
changes.theForH2example,
O and NH 3 molecules
when to attach themselves to the c
excess concentrated
We have anion.
ammonia We have
equilibrium
solution iswithan
added equilibrium
a constant with
by theaexpression:
givencopper(ii)
to pale blue constant given ammonia
sulfate solution, by the expression:
molecules are exchanged for water molecules around the central Cu2+ ion
2+ 4
[[Cu(NH
and the colour changes )4(Hblue.
to a 3deep 2O)2]The][Hreaction
2O] takes place in two stages.
K =
At first the alkaline solution of ammonia 2+ removes
4 protons from the hydrated
copper(ii) ions to give a[Cu(H 2O)precipitate
pale blue 6] [NH3] of the hydrated hydroxide.
[Cu(H 2+ − ! [Cu(H
As2O)
[H6]2O](aq)
is +in2OH
large(aq)
excess 2O)4(OH)2a](s)
and virtually + 2H2O(l)
constant, we can include it in the
pale blue solution pale blue precipitate
equilibrium constant and write:
Then the ligand exchange takes place as the precipitate redissolves to give
the deep blue solution.
[[Cu(NH ) (H O) ]2+]
3 4 2 2
[Cu(H2O) Kstab =
4(OH)2](s) + 4NH3(aq)
pale blue precipitate [Cu(H2O)6][NH3]4
! [Cu(NH3)4(H2O)2]2+(aq) + 2H2O(l) + 2OH−(aq)
where stability constant. Strictly speaking, there are stab
9.125 Cu2+ Withstab
K
Cl— known
is as the
deep blue solution
constants
The ligands NH3 for and each
H2O of arethe equilibria
both unchargedasand H2O molecules
similar in size.are
Thisprogressively substitu
A ligand exchange
allows by NHreaction
exchange 3
also
reactions
molecules, occurs
between
but when
these
here concentrated
we ligands
will without
only a change
consider the in co-
overall constant. The va
hydrochloric
ordinationacid is
numberaddedof to
the copper(ii)
metal sulfate
ion. solution.
Kstab depends on how firmly the ligands bind to the metal atom. In general, ato
A ligandwith
exchange
high reaction also occurs when concentrated
electronegativity hydrochloric acid
This time, the colour changes from pale bluebond weaklyCland
to yellow − ionsthose with lower electronegativity
is added to copper(ii) sulfate solution. This time, as
the colour changes from
replace more
palewater
blue strongly.
molecules
to yellow Cl−Thus
asaround water
thereplace
ions (which
Cu2+ ion. binds via

molecules
water thethe
around very 2+ ion. Tip oxygen at
Cuelectronegative
forms weak bonds while the CN− ion (which binds via the carbon atom that ha A solution of a copper(
[Cu(H2O)6]2+(aq) + 4Cl−(aq) ! [CuCl4]2−(aq) + 6H2O(l)
much lower
pale blue electronegativity) forms
yellow strong bonds and will have a large
green and notvalue
yellow ifo

(see Table 24.4). A high charge on the metal ion also makes K of added chloride
larger; ions
compa
In this case, however, the ligand exchange involves a change in co-ordination stab
This ligand exchange involves
3– a change in co-ordination
4– number. enough to convert all th
number.[[Fe(CN)
Chloride 6] ions
] are[[Fe(CN) .
6] ]water
larger than molecules, so fewer chloride
Chloride ions are 6 and
3+larger– than water molecules,
2+2+ – 6 so fewer chloride ions ions to the yellow chlor
ions can[Fe ][CN the
fit round ] central[Fe ion.]
Cu ][CN
can fit round the central Cu2+ ion.
15.9 Ligand exchange
469983_15_Chem_Y1-2_418-449.indd 435
9.126 Ligand Exchange Reaction of Co2+ With NaOH
_24_A_Chem_BP_397-414.indd 405
The simplest ion that cobalt forms in solution is the pink, [Co(H2O)6]2+
When sodium hydroxide solution is added to aqueous cobalt(II) ions,

hydroxide ions displace water molecules from hydrated cobalt(II) ions
forming a precipitate of cobalt (II) hydroxide.
[Co(H2O)6]2+(aq) + 2OH—(aq) → [Co(H2O)4(OH)2](s) + 2H2O(l)

pink solution blue ppt.
 
We see a blue precipitate of cobalt(II) hydroxide forming, which turns
pink/red when warmed if the alkali is in excess.

47
43
9.127 Co2+ With NH3

When excess concentrated ammonia solution is added to pink cobalt(II)
solution, [Co(H2O)6]2+, six ammonia molecules are exchanged for all six
water molecules around the central Co2+ ion.
[Co(H2O)6]2+ (aq) + 6NH3 (aq) ⇌ [Co(NH3)6]2+ (aq) + 6H2O (l)

pink solution brown solution
 
The pink solution turns brown.
9.128 Co2+ With Cl—

A ligand exchange reaction also occurs when concentrated
hydrochloric acid is added to cobalt(II) sulfate solution.
This time, the colour of the solution changes from pink to blue as Cl−
ions replace water molecules around the Co2+ ion.
[Co(H2O)6]2+ (aq) + 4Cl— (aq) ⇌ [CoCl4]2— (aq) + 6H2O (aq)

pink solution blue solution
9.129 Stability Constant/Kstab

If Kc is divided by the concentration of water molecules in the ligand
exchange reaction, we get Kstab.
[CuH2O)6]2+ + 4Cl- ⇌ [CuCl4]2- + 6H2O
([CuCl4]2-)(H2O)6
Kc =
([CuH2O)6]2+)(Cl-)4
Kc ([CuCl4]2-)
= = Kstab
(H2O)6 ([CuH2O)6]2+)(Cl-)4

48
44
9.130 Relative Stability of Complex Ions

In aqueous solution, the simple compounds of most transition metals
contain complex ions with formulae such as [Cu(H2O)6]2+ and
[Co(H2O)6]2+.
When solutions containing other ligands, such as Cl—, are added to

aqueous solutions of these hydrated cations, the mixture comes to an
equilibrium in which the water molecules of some complexes have
been replaced by the added ligands.

For example, the equilibrium which results when concentrated sodium
chloride solution is added to aqueous cobalt(ii) ions is:
[Co(H2O)6]2+ (aq) + 4Cl— (aq) ⇌ [CoCl4]2— (aq) + 6H2O (l)
The equilibrium constant, Kc, for this reaction is:

Kc = [[CoCl4]2—][6H2O]4
[[Co(H2O)6]2+][Cl—]4

Kc = [[CoCl4]2—][6H2O]4
[[Co(H2O)6]2+][Cl—]4
[H2O(l)] is constant and therefore it is not included in the equation for
Kc.
Kstab = [[CoCl4] ]
2—
[[Co(H2O)6]2+][Cl—]4
Equilibrium constants like this for the formation of complex ions in
aqueous solution are called stability constants and the symbol Kstab is
sometimes used in place of Kc.

49
45
9.133 Stability Constants

The stability constant is the equilibrium constant for the formation of the
complex ion in a solvent from its constituent ions or molecules.
Stability constants enable chemists to compare the stabilities of the

complex ions of a cation with different ligands.
The reaction to which Kstab relates always involves the displacement of

a solvent ligand, most frequently H2O.
The larger the stability constant, the more stable is the complex ion
compared with that containing water.
9.134 Stability Constants

The values quoted usually give the stability of the complex relative to
the aqueous ion where the ligand is water.
C CHEMISTRY
The higher the value of the stability constant, the more stable the
complex.
which the water molecules of some complexes have been replaced by the
added ligands. For example, the equilibrium which results when concentrated
alues of Kstab for some Complex
e values are usually so large that sodium chloride solution isKadded
stab logions
to aqueous copper(ii) Kstabis:
given in the form logKstab. [CuCl 4]2− 4.2 × 105 5.62
[Cu(H2+2O)6]2+(aq) + 4Cl−(aq) ! 2−
13 [CuCl4] (aq) + 6H 2O(l)
[Cu(NH3)4] 1.3 × 10 13.1
The equilibrium
[Fe(CN)6]
3− Kc×, for
constant, 10 1031this reaction is: 31
[Fe(CN)6]4− 1.0 × 1024 24
[Ag(NH + [CuCl42–(aq)]
1.7 × 107 7.23
K =3 )2 ]
c
[Cu(H2O)6 (aq)][Cl–(aq)]4
2+
[H2O(l)] is constant and therefore it is not included in the equation for Kc.
Now try this
Equilibrium constants like this for the formation of complex ions in aqueous
solution are called stability constants and the symbol K = 0.050
1 A solution of copper sulfate had ammonia added until [NH3] stab
is sometimes
mol dm–3.
used
9. 135 Stability
inCalculate
place of the Constants
Kc.ratio of [Cu(NH3)4(H2O)2]
2+
to [Cu(H2O)6] under these conditions.
2 (Harder – use the Nernst equation on page 389.)
Stability constants enable chemists to compare the stabilities of the complex
The Efollowing Fe3+table
e− shows
+with Fe2+ isthe stability
+0.77 constants of three complexes of
ions ofcella for V
1
cation different ligands. The larger the stability constant, the
the
morecopper(ii) 1 ion.
stableE is the
Calculate for complex 3− −
+ e compared
[Fe(CN) ] ion )]4−. that containing water.
[Fe(CN with
cell 6 6
These show
Table 15.4 thatthe
shows thestability
relativeconstants
stabilities of thecomplexes
of three three copper(ii) complexes
of the copper(ii) ion.
These
are:
show that the relative stabilities of the three copper(ii) complexes are:
2− > O)2]2+ >occurs
[Cu(NH3)4(H2reaction [CuCl 2− concentrated hydrochloric
[Cu(EDTA)] 4]
A more complicated ligand-exchange when
acid is added to aqueous Cu ions. Here, four H2O ligands are replaced by Cl −
2+
Ligand Complex ion K leaving the tetrahedral Table 15.4 The stability constants of three
ions, but the remaining two water molecules are expelled,
Cl 5 copper(ii) complexes.
tetrachlorocopper(II) ion (see[CuCl 4] 24.9):
Figure 4.0 × 10
NH3 [Cu(NH ) (H O) ]2+ 1.3 × 1013
Cu(H2O)62+(aq) + 4Cl −(aq) → 3[CuCl
4 2 22−
4] (aq) + 2H2O(l)
EDTA [Cu(EDTA)] 6.3 × 1018
Solutions containing a the a

Complex ions and entropy
b
n and b the [CuCl 4]2− ion
When a bidentate ligand, such as 1,2-diaminoethane, replaces a monodentate
ligand, such as water, there is an increase in entropy of the system. One
molecule of the bidentate ligand replaces two molecules of the monodentate
ligand and this results in an increase in the number of product particles. For
example, in the reaction:
[Cu(H2O)6]2+(aq) + 3H2NCH2CH2NH2(aq)
→ [Cu(H2NCH2CH2NH2)3]2+(aq) + 6H 2O(l)
there are seven product particles but only four reactant particles. In this
reaction the enthalpy change is very small and so the entropy change in the
surroundings is close to zero.
As the entropy of any system depends on the number of particles present, the
al A Level Chemistry 50
46
stant are worked out in the

QUESTION
9.136 Skill Check
c (see page 124). For example,
7 a Write expressions for the stability constants for the
(mol dm ) –3 following reactions:
__ _____________________
)]4 (mol dm–3) × (mol dm–3)4 i [PtCl4]2–(aq) + 2NH3(aq)
PtCl2(NH3)2(aq) + 2Cl–(aq)
ii [Cr(H2O)6]3+(aq) + 2Cl–(aq)
ven on a log10 scale. When
[Cr(H2O)4Cl2]+(aq) + 2H2O(l)
y have no units. Stability
are the stability of any two iii [Ni(H2O)6]2+(aq) + 4NH3(aq)
ally give the stability of the [Ni(NH3)4(H2O)2]2+(aq) + 4H2O(l)
s ion where the ligand is b An iron(III) ion, Fe3+, in aqueous solution has six
the stability constant, the water molecules bonded to it as ligands.
e 24.5 gives some values i Draw the structure of this ion.
us copper(II) complexes
ii When thiocyanate ions, SCN–, are added to
9.137anColour in Complex
aqueous solution Ionions, the
of iron(III)
solution turns red and one water molecule is
log10 Kstab Transition metalby
replaced have it’s outermost
a thiocyanate ion.electrons in the d-orbitals. Some
Use the concept
along the
of stability constants to explain why the
axes, and others between the axes.

5.6
reaction
Ligands occurs.
also have an electron cloud around them. When a ligand’s lone
13.1
iiiforms
pair Deduce the formula
a dative of the
bond with the ion forming
metal the is bound to be
ion, there
16.9 red solution.
CO2– repulsion between the two electron clouds i.e. the electrons in the d
orbitals
iv The and the electron
stability cloud
constant foraround
aqueous theFe
ligands.
3+ ions
OH with SCN– as a ligand is 891 dm3 mol–1. The

stability constant for aqueous Fe3+ ions with
OH 25.0 fluoride ions, F–, as a ligand is 2 × 105 dm3 mol–1.
A solution containing fluoride ions is added to
OH the red solution. Would you expect to observe
any changes? Explain your answer.
nts of some complexes
9.138 Colour in Complex Ion

in general, complexes
benzoate and
The colour of complexes
Colour, which is a characteristic property of transition metals, results
due to
You cannot failthis
torepulsion
notice the between thecolours
striking electrons
ofofcomplexes
the ligands and electrons
gher stability constants than of the partially filled d-sublevel of the central metal ion.
containing transition metal ions. But how do these colours
s. We can use the values of
arise? White light is made up of all the colours of the
t the effect of adding different
visible spectrum. When a solution containing a transition
ample, the addition of excess
2– metal ion in a complex appears coloured, part of the
4] (aq) should result in the
visible spectrum is absorbed by the solution. However, that
n of the ammonia complex
still doesn’t explain why part of the spectrum is absorbed
f the ammonia complex is
by transition metal ions. To answer this question we must
complex. The position of
look in more detail at the d orbitals in the ions.
ht in the direction of the more
The five d orbitals in an isolated transition metal atom
ess 1,2-dihydroxybenzene
or ion are described as degenerate, meaning they are all at
plex results in the formation
the same energy level (Figure 24.13).
ydroxybenzene. This is
In the presence of ligands a transition metal ion is
ith the 1,2-dihydroxybenzene
not isolated. The co-ordinate bonding from the ligands
a:
2– causes the five d orbitals in the transition metal ion to
O O Marginalizer Bilal Hameed
Cu + 4H++ 4NH4+ split into two sets of non-degenerate orbitals at slightly
O O Transition Elements different energy levels (Figure 24.14). In a complex with six Bilal Hameed
z z z
51
47
y y y
x x
x
dyz dxz dxy
9.139 Colour in Complex Ion z z
This repulsion will vary between the two orbital systems as they are not
y
repelled equally by the electrons of the ligand. One orbital
y system will
x
be repelled more than the other, causing the electrons in the d sublevel
x
to become unstable and split into two different
dx –y energy levels.
dz 2 2 2
Each energy
Figure level
24.13 contains onlyd one
The degenerate type
orbitals of orbitalmetal
in a transition system
atom. i.e. either 2
orbital or 3 orbital, but never both. The orbitals that are repelled more
will be atligands,
a higher energy
the ligands arelevel andinthe
arranged an one’s repelled
octahedral shape less will
in a be at a with ligands. The difference in the energy
complex
aroundlevel.
lower energy the central metal ion. The lone pairs donated by between the non-degenerate d orbitals is labelled ΔE. ΔE is
the ligands into the transition metal ion repel electrons in part of the visible spectrum of light. So, when light shines
the two d x2–y2 and d z 2 orbitals shown in Figure 24.13 more on the solution containing the Cu(H2O)62+ complex,
than those in the other three d orbitals. This is because an electron absorbs this amount of energy. It uses this
these d orbitals line up with the co-ordinate bonds in energy to jump into the higher of the two non-degenerate 377
the complex’s octahedral shape and so theyChapter are closer24:
to Transition elements
energy levels. In copper complexes, the rest of the visible
the bonding electrons in the octahedral arrangement, spectrum that passes through the solution makes it appear
increasing repulsion between electrons. Therefore the blue in colour.
z
orbitals are split, with these
z two d orbitals at a slightly
z The exact energy difference (ΔE) between the non-
higher energy level than the dyz, d xz and d xy orbitals degenerate d orbitals in a transition metal ion is affected
Splitting
9.140 (Figure 24.14). of the D-Orbital by many factors. One of these factors is the identity of the
A Cu2+ ion has an electronic confi y guration of ligands that surround the transition metal ion. As you
y y
In a simple
[Ar] metal ion,24.14
3d9. Figure xthe shows
five 3dhoworbitals
the nine all have the
dx electrons aresame have
energy
seen,and
a solution containing Cu(H2O)62+ is a light blue,
x
are saiddistributed between the non-degenerate
to be degenerate, orbitals formed
but in the presence of ligands, whereas a solution containing Cu(NH3)2(H2O)22+ is a very
the orbitals
dyz dxz dxy
divide into two energy
z
levels and are znow known as non degenerate excited electron
orbitals. absorbs energy
∆E
dx 2–y 2 dz 2
y
y
3d x ∆E
x energy absorbed
dx2–y
2
Cu2+(...3d9) dz2 from visible spectrum
degenerate that corresponds
3d orbitals to ∆E
Figure 24.13 The degenerate d orbitals in a transition metal atom. dyz dxz dxy
splitting the the energy absorbed can be
ligands, the ligands are arranged in an octahedral shape in a complex withd orbitals
ligands.to Th
give
e difference in the energy worked out by the equation:
around the central metal ion. The lone pairs donated by non-degenerate
between the non-degenerate d orbitals is labelled ΔE. ΔE is
orbitals ∆E = hν
the ligands into the transition metal ion repel electrons in part of the visible spectrum of light. So, when light shines
the two d x2–y2 and d z 2 orbitals shown in Figure 24.13 more on the solution containing the Cu(H2O)62+ complex, where ν is the frequency
than those in the other three d orbitals. This is because an electron absorbs this amount of energy. It uses this of light absorbed and
h is Planck’s constant
the complex’s octahedral shape and so they are closer to energy levels. In copper complexes, the rest of the visible
Figure 24.14 The splitting of the 3d orbitals in a Cu(H2O)62+ complex ion.
the bonding electrons in the octahedral arrangement, spectrum that passes through the solution makes it appear
9.141 Splitting of the D-Orbital
increasing repulsion between electrons. Therefore the
orbitals are split, with these two d orbitals at a slightly
blue in colour.
The exact energy difference (ΔE) between the non-
(Figure 24.14). Both in degenerate and non by degenerate 3d of
many factors. One orbitals,
these factorstheis the
electrons
identity of are
the in
their ground
A Cu2+ ion has an electronic state.
configuration of However, ligands
for a that
complex
surroundion to exhibit
the transition metalcolour,
ion. As you
[Ar] 3d9. Figure 24.14 shows how the nine d electrons are have seen, a solution containing Cu(H2O)62+ is a light blue,
electrons must be excited enough
distributed between the non-degenerate orbitals formed
to transit from a lower energy state
whereas a solution containing Cu(NH3)2(H2O)22+ is a very
to a higher energy state by absorbing energy.
excited electron
absorbs energy
For this to happen the metal ∆E
dx –y dz2 2 2
3d
therefore has to have a partially filled
∆E
d orbital. energy absorbed
Cu2+(...3d9) from visible spectrum
3d orbitals to ∆E
dyz dxz dxy
d orbitals to give worked out by the equation:
non-degenerate
orbitals ∆E = hν
where ν is the frequency

of light absorbed and

52
48
9.142 Splitting of the D-Orbital

The energy gap created due to repulsion is very small and requires only
a small amount of energy for the electrons in the lower energy level to
be excited enough to jump to a higher energy level. This energy is
obtained from the visible light spectra.
The light spectra is not one energy but a series of colours having
different energies.
Chapter 24: Transition elem
Electrons absorb energy in the form of some colours, while we see the
complimentary colours that were not absorbed.
z z z
y y y
x x
x
dyz dxz dxy
z z
9.143 Octahedral Complex Ion
The lone pair of ligands form the dative bonds of the complex ions. In y
y
an octahedral complex, these bonds are along the x,y and z axes.x
The electrons from these bonds start to repel dthe

x –y electrons of the d
2 2 dz2
orbitals of the metal ion.
Figure 24.13 The degenerate d orbitals in a transition metal atom.

The orbitals that were along the axes, dx2—y2 and dz2 are repelled
ligands,
more than the the ligands
orbitals are arranged
that were in anthe
between octahedral
axes, shape in a dyz.
dxy, dxz and complex with ligands. The difference in the ener
around the central metal ion. The lone pairs donated by between the non-degenerate d orbitals is labelled ΔE
the ligands into the transition metal ion repel electrons in part of the visible spectrum of light. So, when light sh
the two d x2–y2 and d z 2 orbitals shown in Figure 24.13 more on the solution containing the Cu(H2O)62+ complex,
than those in the other three d orbitals. This is because an electron absorbs this amount of energy. It uses th
these d orbitals line up with the co-ordinate bonds in energy to jump into the higher of the two non-degen
the complex’s octahedral shape and so they are closer to energy levels. In copper complexes, the rest of the vis
the bonding electrons in the octahedral arrangement, spectrum that passes through the solution makes it a
orbitals are split, with these two d orbitals at a slightly The exact energy difference (ΔE) between the non
higher energy level than the dyz, d xz and d xy orbitals degenerate d orbitals in a transition metal ion is affec
(Figure 24.14). by many factors. One of these factors is the identity o
A Cu2+ ion has an electronic configuration of ligands that surround the transition metal ion. As yo
[Ar] 3d9. Figure 24.14 shows how the nine d electrons are have seen, a solution containing Cu(H2O)62+ is a ligh
Therefore, the 2 orbital
distributed system
between moves to a higher
the non-degenerate orbitals energy
formed level whereas
and thea solution
3 containing Cu(NH3)2(H2O)22+ is a
orbital system moves to a lower energy level in the non-degenerate
orbitals excited el
absorbs e
∆E
dx 2–y 2 dz 2
3d ∆E
energy absorbed
Cu2+(...3d9) from visible spectrum
3d orbitals to ∆E
dyz dxz dxy
non-degenerate
orbitals ∆E = hν


53
Transition Metals 49 2815 5
Splitting of
Chapter 24: Transition elements
d orbitals Placing ligands around a central metal ion changes the energies of the d orbitals
Some of the d orbitals gain energy and some lose energy
9.145 Octahedral
z
Complex
z
Ion z
The amount of splitting depends on the • central ion

Without forming the complex ion, the d orbitals are degenerate and • ligand
y
don’t have any colour. Buty once
x they form a complex
x ion,y the d orbital
x
becomes non degenerate.
The difference in energy between the new levels affects how much energy
d d
yz d xz xy
will be absorbed when an electron is promoted to a higher level.
z z
This energy gap is small enough that electrons in the lower energy level
The amount of energy will govern the colour of light which will be absorbed.
can move to a higher energy level by gaining energy
y from the visible
y
light spectra.
x
x
dx2–y2 dz2
two 3d orbitals of higher energy
Figure 24.13 The degenerate d orbitals in a transition metal atom.

z2, x2-y2
ligands, the ligands are arranged in an octahedral shape in a complex with ligands. The difference in the energy
around the central metal ion. The lone pairs donated by between the non-degenerate
of equal denergy
orbitals is labelled ΔE. ΔE is
the ligands into the transition metal ion repel electrons in
five 3d orbitals
part of the visible spectrum of light. So, when light shines
OCTAHEDRAL
the two d x2–y2 and d z 2 orbitals shown in Figure 24.13 more on the solution containing the Cu(H2O)62+ complex, COMPLEX
than those in the other three d orbitals. This is because an electron absorbs this amount of energy. It uses this
the complex’s octahedral shape and so they are closer to energy levels. In copper complexes, the rest of the visible
the bonding electrons in the octahedral arrangement, spectrum that passes through the solution makes it appear xy, xz, yz
orbitals are split, with these two d orbitals at a slightly The exact energy difference (ΔE) between the non-
three 3d orbitals of lower energy
(Figure 24.14).
A Cu2+ ion has an electronic configuration of
by many factors. One of these factors is the identity of the
ligands that surround the transition metal ion. As you
[Ar] 3d9. Figure 24.14 shows how the nine d electrons are have seen, a solution containing Cu(H2O)62+ is a light blue,
distributed between the non-degenerate orbitals formed whereas a solution containing Cu(NH3)2(H2O)22+ is a very
three 3d orbitals of higher energy
excited electron
absorbs energy
five 3d orbitals of equal energy
∆E
z2, x2-y2
dx 2–y 2 dz 2
3d
TETRAHEDRAL
∆E
Cu2+(...3d9)
energy absorbed
from visible spectrum
COMPLEX
degenerate that corresponds xy, xz, yz
3d orbitals to ∆E
dyz dxz dxy
splitting the
two can
the energy absorbed 3dbeorbitals of lower energy
non-degenerate
orbitals ∆E = hν

Figure 24.14 The splitting of the 3d orbitals in a Cu(H2O)62+ complex ion. Absorbed colour λ nm Observed colour λ nm
VIOLET 400 GREEN-YELLOW 560

BLUE 450 YELLOW 600
BLUE-GREEN 490 RED 620
YELLOW-GREEN 570 VIOLET 410
YELLOW 580 DARK BLUE 430
ORANGE 600 BLUE 450
9.147 Octahedral ComplexRED
Ion 650 GREEN 520
The colour seen is a solution of copper(II)sulphate is blue because What colour is this
white light minus the red and yellow wavelengths are absorbed hexaaqua complex?
colour being absorbed.
In case of Cu, it
absorbs the red-
Absorbance
Absorbance
orange frequency, and

we see the
complementary colour,
blue, that was not wavelength (nm) wavelength (nm)
300 400 500 600 700 800 300 400 500 600 700 800
absorbed. blue green yellow red blue green yellow red

54
50
9.148 Theory of Colour Gradient

A colourless solution appears such because no colour is being
absorbed, and light passes through the solution. But when some light is
absorbed, the solution appears to be coloured.
The strength of the colour is determined by how much absorption of it’s

complimentary colour is occurring. The more the absorption, the
deeper the colour and vice versa.
Energy in the form of a certain frequency of visible light can be

absorbed to promote an electron from the lower set of orbitals to the
higher set: The d orbitals are split in different
ways in different-shaped complex ions.
9.149 Theory of Colour Gradient

Cu with H2O appears pale blue because it absorbs lesser red-orange
When white light travels through copper sulfate solution, orange light
frequency compared topromoting
is absorbed, Cu with NHfrom
an electron thewhich
3(aq), absorbs
lower set of more of the red-
d orbitals to the
higher set. This means that the light coming out contains all the colours For a substance to appear
24
orange frequency and
of the thus
spectrum appears
except orange and sodeep blue.
appears blue, the complementary coloured, certain frequencies of
The 3d block
colour to orange. light in the visible region of the
spectrum must be absorbed.
DNA replication, particularly in cancer cells that are undergoing rapid cell division,Formation of coloured complex
and the cell dies. There is no obvious reason why trans-platin is ineffective; one ions/compounds requires the
theory is that it becomes deactivated before it can attach itself to DNA. presence of a partially filled d
subshell.
24.5 Colour in the d block

White light is a mixture of all
The origin of colour colours (frequencies) of visible
light.
All atoms and molecules absorb in the ultraviolet region of the spectrum because this
radiation has enough energy to excite their outer electrons. The ultraviolet region is
3+ 4+
Let us consider
outside the visible range ofthetheScspectrum,
ion or the
so Ti ion. These
absorption bothultraviolet
in the have no leaves a
substance electrons in the
colourless. Some3d subshell and so
substances, are colourless,
however, as it isouter
also have not possible
electrontolevels that
absorbclose
are sufficiently energy to promote
together a 3d electron.
for visible radiation to have enough energy to bring about
The Cu+ ion and the Zn2+ ion both have 10 3d electrons (Figure
electronic excitation. Under these circumstances, the substance appears coloured. The
4.29), and as there is no space in the upper set of orbitals it is not possible
resulting colour seen is white light minus the colour being absorbed. The colour we see
to promote an electron to the upper set of orbitals. No light in the visible
is therefore the complementary
region colour toand
of the spectrum is absorbed, thethese
colour
ionsbeing absorbed (see Figure 24.14).
are colourless.
To absorb in the visible region, the substance must have two energy levels that
are very close together. Close energy levels come about in two ways, namely charge
9.150 Prediction of Colour
transfer and d-to-dWhat do we mean when we say that a solution of copper
transitions.
sulfate is blue? Is blueness a property of copper sulfate
solution, or is the blueness in our minds? What colour
Figure 24.14 The colours observed when Example Absorption spectrum Colour Cr2O72− (orange), CrO42− (yellow)
Colour observed
absorption takes place in the visible region of would copper sulfate solution be in orange light? Or in the dark? (complementary)
absorbed and MnO− (purple) are all very
4
the spectrum highly coloured, but they have no d
electrons. They are coloured because
absorption
of a different mechanism from the one

The elements and their compounds/complexes can act as catalysts. For described here.
example, finely divided iron is the catalyst in the Habergreen
process for the
purple
KMnO
production
4 of ammonia:
N2(g) + 3H2(g) 2NH3(g)
blue yellow
K2CrO4
red blue
CuSO4.5H2O
400 700
wavelength/nm
Charge transfer
If a substance contains bonds which are on the borderline between ionic and
25_11 Cam/Chem
covalent, it may AS&A2
change from one bonding type to another by absorbing visible
light. This effect is shown by some solids which are coloured (for example PbO,
Barking Dog Art
which is orange, and AgI, which is yellow) even though the ions they contain are
colourless. In the d block, another example is CuO, which is black even though the
Cu2+ ion is blue.
d-to-d transitions
Marginalizer In the d block, colour usually arises because of d-to-d electronic transitions. The t2g and Bilal Hameed
the eg orbitals are close in energy, and electrons in the t2g orbitals may be excited into
the eg orbitals by the absorption of a photon of visible light. Using the Planck equation,
∆E = hf
the frequency associated with the energy difference between the orbitals (∆E in
Figure 24.7) corresponds to the frequencies of visible light.
411
same experimental
Transition metal complexes do not obey valence shell electron to them – to what e
pair repulsion (VSEPR) theory rules, so although
55 six coordinate scientific knowledg
51 and to what extent
complexes are virtually always octahedral, four coordinate
complexes may be tetrahedral or square planar. of interpretation an
9.151 Tetrahedral Complex Ion
In a tetrahedral the complex ions the bonds are not along the axes, but
rather, are found between the axes.Thus the dx2-y2 and dz2 are not
repelled as strongly as they were in an octahedral complex. And dxy,
dxz and dyz are repelled more strongly.
Therefore the dxy, dxz and dyz orbitals will move to a higher energy
level and dx2-y2 and dz2 will move to a lower energy level. And electrons
will transition from the 2 orbital system to the 3 orbital system.

For example in CuCl42- the bonds are not along the axes

2. 61 Tetrahedral Complex Ion
The degenerate orbitals therefore split into a higher 3 orbital and lower 2
The degenerate
orbital orbitalsonce
degenerate orbitals therefore split into
the complex ionaishigher 3 orbital and lower 2
formed.
orbital degenerate orbitals once the complex ion is formed.
dxy dxz dyz

Tetrahedral
⇅ ⇅
⇅ ⇅ CuCl42- Complex
3d9
Cu2+ Before complex ⇅ ⇅

⇅ ⇅
dx2-y2 dz2

56

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1

12 An introduction to the chemistry of transition elements

12.3 Colour of complexes

12.4 Stereoisomerism in transition element complexes

12.5 Stability constants, Kstab

12 An introduction to the chemistry of transition elements

32 www.cie.org.uk/alevel Back to contents page

12.4 Stereoisomerism in a) describe the types of stereoisomerism shown by complexes,

Back to contents page www.cie.org.uk/alevel 33

13.1 First-row d-block elements – the transition elements

23.1 The general propert

■ Figure 13.1 Position Group 1 2 13 14 15 16 17 18

9.2 d-block elements

Hint Electronic configurations in

Figure 2 shows the electron arrangem

From potassium onwards, the orbitals of highest energy in the third

The transition elements

3p (max. : 6 electrons in 3 orbitals)

3s (max. : 2 electrons in 1 orbital)

Notice the unexpected electron configurations of chromium and copper.

s,p,d,f notation Electrons-in-boxes

of copper, [Ar]3d10 4s1, with a filled 3d

from one element to the next.

Bilal Hameed Transition Elements

9.10 ions of d-block elements

However, once the 3d level is occupied by electrons, these repel the 4s

The 4s electrons are therefore pushed to a higher energy level, higher

9.11 ions of d-block elements 13.1 First-row d-block elements 453

■ Figure 13.3 The 3d

9.16 Skill check 7

number of unpaired electrons

(b) Solid potassium manganate(VII), KMnO4, decomposes on heating to form

Construct an equation for this reaction.

(c) Explain the origin of colour in transition element complexes.

9.18 What is a transition element?

The simple definition of transition metals as ‘d-block elements’ is

Transition Elements Bilal Hameed

9.19 What is a transition element?

• Their compounds are usually white, unlike the compounds of

• They show little catalytic activity.

9.20 What is a transition element?

9.21 d-block elements

Therefore, electrons of an element with ions having completely empty

Bilal Hameed Transition Elements

3 The transition metals

onic structure. b iii Which electrons would are lost you

9.25 Characteristics of the transition elements

They show variable oxidation numbers in their compounds.

They form coloured ions in solution.

They can act as catalysts both as the elements and as their

They form complex ions.

9.26 Physical & Atomic Properties

9.27 Melting points

The conductivities of the 3d-block metals are similar to those of

Bilal Hameed Transition Elements

9.28 Atomic radii of d-block elements

Because of their similarity it is possible to draw up a list of

The increasing number of outer-shell electrons from sodium to argon

9.30 Atomic radii of d-block elements

So while the nuclear charge is increasing across the period in the d-