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 Co-ordination Compounds

Molecular or addition compounds:

When solutions containing two or more stable compounds in some molecular proportions
are allowed to evaporate, crystals of new substance are obtained. These substances are
termed as molecular or addition compounds.

ex:

KCl + MgCl2 + 6H2O ⎯⎯

→ KCl.MgCl2 .6H2O
FeSO4 + Al2(SO4 )3 + 24H2O ⎯⎯
→ FeSO4 .Al2(SO4 )3 .24H2O
4KCN + Fe(CN)2 ⎯⎯
→ 4KCN.Fe(CN)2
CuSO4 + 4NH3 ⎯⎯
→ CuSO4 .4NH3

Molecular or addition compounds are of two type.

(I) Double salts or lattice compounds: The addition compounds which are stable in the
solid state only but are broken down into individual constituents when dissolved in water
are called double salts or lattice compounds.

for examples when mohr's salt FeSO4 .(NH4 )2 SO4 .6H2O is dissolved in water, it exhibits
the properties of FeSO4 and (NH4)SO4 i.e. they produced Fe2+ ,NH4+ ,SO24− ions in solutions.
Thus each ion has its identity in double salt
2+
FeSO4 .(NH4 )2 SO4 .6H2O ⎯⎯
→ Fe(aq) +
+ NH4(aq) + 2SO24(aq)
−
+ 6H2O

(I)Coordination compound: the addition compounds in which some of the constituent ions
or molecules lose their identity and when dissolved in water they do not break up
completely into individual ions are called coordination or Complex compounds.

For example- when crystal of CuSO4.4NH3 are dissolved in water, there is no evidence for the
presence of Cu2+ ions and ammonia molecules. A new iron is produced in which Ammonia
molecule or directly linked with the metal ions [Cu(NH3)4]2+ is produced in which ammonia
molecule are directly linked with the metal ions.

Thus a coordination or complex compound may be defined as a molecular compound that

result from the combination of two or more, simple stable molecule compound and retains
its identity in the solid as well as in the dissolved state.

Structure of complex compounds

 Transition
Metal Ligand

K3 [Fe(CN)6]

Cation
Co-ordination
sphere

Terminology of complex compound

(I) Ligand: The neutral molecule or an ion which are directly linked with the central metal
atom or ion in a complex ion are called ligands. The legends are attached to the central metal
ion atom through co-ordinate bonds a dative linkage. Ligand acts as a donor as it donates one
or more electron pairs to the central metal atoms or ions which acts as an acceptor. The
ligand thus acts as lewis base and central metal (ion) acts as Lewis acid.

Types of ligands:

(a) Mono or uni dentate ligand: They supply only one electron pair to central metal
atom/ion. ex: F − ,Cl − ,Br − ,H2O,NH3 ,CN− ,NO2− ,OH− ,CO etc

(b) Bidentate ligands: Ligands which have two donor atoms and have ability to link with
central metal ions at two positions are called bidentate ligands.ex:

Chelating ligand: A multidentate ligand is known as chelating (chelate is greek word

meaning crab) ligand if on coordination it result in the formation of a closed or cyclic ring.
The complex thus formed are called chelates are comparatively more stable than ordinary
complex.

Chelation therapy is a therapy which is used in cases of

acute lead poisoning (as in bullet wounds). A chelating
agent is a molecule with at least two negatively charged
groups that allow it to form complexes with metal ions with
multiple positive charges, such as lead. The chelate that is
thus formed is nontoxic and can be excreted in the
urine. The chelating agents used for treatment of lead
poisoning are edetate disodium calcium (CaNa2EDTA),
Dimercaprol etc. which are injected.

EDTA
Flexidentate character: Polydentate ligands have flexidentate character.

EDTA: 6 usually but 5,4 and 3 also in different acidic medium.

Similarly sulphate ion can acts as monodentate ligand.

Ambidentate ligands: There are certain ligands which have two or more donor atoms but in
forming complexes only one donor atom is attached to metal ion. Such ligands are called
ambidentate ligands.

: NO2 Nitro (Nitrito − N) : ONO Nitrito (Nitrito − O)

: CN Cyanido(Cyanido − C) : NC Isocyano (Cyanido − N)
: SCN Thiocyanato : NCS IsoThiocyanato

Note: These types of ligands can show linkage isomerism.

Coordination Number: The number of atoms of ligands that are directly linked to the central
metal atom by coordinate bond is known as the coordination num,ber of the metal atom.
Complex C.N
[Cu(NH3 )4 ]2+ 4
[Co(en)3 ]3+ 6

The most common coordination number exhibited by metal atoms is 2,4 or 6.

It has been observed that in a particular oxidation state a metal prefer to exhibit the same
coordination number.

Coordination sphere: The central metal atom and the ligand are directly attached to it are
enclosed in a square bracket.This has been called coordination sphere.It behave as single
unit because the ligand present in the coordination sphere are held tightly by metal ion.

→ 4K + + [Fe(CN)6 ]4 −
K 4[Fe(CN)6 ] ⎯⎯
Coordination sphere

The charge on the coordination sphere is the alzebric sum of the charge carried by central
metal ion and the ligand attached to it.

Nomenclature of Coordination compound:

IUPAC has published rules for systemetaic naming for coordination compound.

Rules:
(1) If a complex compound is ionic, the name of cation is given first, just like naming a simple
salt.

(2) Within a complex sphere, the ligand are named first followed by the metal ion

Name of ligand:

(I) Anionic ligand ending with ide: ending letter ‘e’ or’ ide’ is replaced by ‘o’

Anion Symbol Name as Ligand

Chloride Cl − Chlorido or Chloro
Bromide Br − Bromido or Bromo
Cyanide CN− Cyano
Oxide O2− Oxo
Peroxide O22− Peroxo
Hydroxide OH− Hydroxo
Sulphide S2− Sulphido
Amide NH2− Amido
Nitride N3− Nitrido
Phosphide P3− Phosphido
hydride H− hydrido
Azide N3− Azido

Compounds containing cationic complex ion:

Complex compound Name

[Pt(NH3 )6 ]Cl4 Hexaammine platinum(IV) chloride
[Co(NH3 )4 H2OCl]Cl2 Tetraammineaquochloro cobalt(III) Chloride
[Cu(en)2 ]SO4 Bis-(ethylenediamine) copper(II) Sulphate
[Cr(H2O)4 Cl2 ]+ Tetraaquodichloro Chromium(III) ion
[Fe(H2O)4 (C2O4 )]2 SO4 Tetraaquooxalato iron(III) Sulphate
[Cr(NH3 )4 (ONO)Cl]NO3 Tetraamminechloronitrito chromium(III)
Nitrate
[Ag(NH3 )2 ]Cl Diammine silver(I) Chloride
[Co(NH3 )5(NCS)]Cl2 Pentaammineisothiocyanato cobalt(III)
Chloride

Complex compound Name

Ku[Fe(CN)6 ] Potassium Hexacyano ferrate(II)
K3[Cr(C2O4 )3 ] Potassium Trioxalato chromate(III)
K3[Co(C2O4 )2 Cl2 ] Potassium Dichlorodioxalato cobaltate(III)
K 2HgI4 Potassium tetraiodo mercurate(II)
K 2[PtCl6 ] Potassium Hexachloro platinate(IV)
LiAlH4 Lithium tetrahydrido aluminate(III)
[Ni(CN)4 ]2− Tetracyano nickelate(II) ion
K3[Fe(CN)5 NO] Potassium pentacyanonitrosyl ferrate(II)

Complex Compound Name

[Cr(NH3 )6 ][Co(CN)6 ] Hexaammine chromium
[Pt(NH3 )4 ][CuCl4 ]
[Cr(NH3 )6 ][Co(C2O4 )3 ]
[Pt(Py)4 ][PtCl4 ]

Writing the name of Mononuclear Coordination Compounds:

The following rules are followed when naming coordination compounds:
(i) Like simple salts the cation is named first in both positively and negatively charged
coordination entities.
Examples :
[Ag(NH3)2]Cl, diamminesilver(I) chloride. K3[Fe(CN)6],potassium hexacyanidoferrate(III).

(ii) The ligands are named in an alphabetical order (according to the name of ligand, not the
prefix) before the name of the central atom/ion.
Examples :
[Pt(NH3)BrCl(CH3NH2)], amminebromidochloridomethylamineplatinum(II).
[Co(H2O)2(ox)2]–, diaquabis(oxalato)cobaltate(III).

(iii) Names of the anionic ligands end in –o and those of neutral ligands are the same except

H2O aqua
NH3 ammine
CO carbonyl
CS thiocarbonyl
NO nitrosyl

Note: In the case of polydentate ligand we use single ‘m’ in the spelling
(IV) Posetively charged ligand have suffix ium

NO+ Nitrosylium
: NH2 − NH3+ (N2H5+ ) Hydrazinium
Cl + Chloronium

Some more important examples of neutral and cationic ligands are :

P4 tetraphosphorus
O2 dioxygen
S8 Octasulphur
CO(NH2)2 urea

(v) Prefixes mono, di, tri, etc., are used to indicate the number of the one kind of ligands in
the coordination entity. When the names of the ligands include a numerical prefix or are
complicated or whenever the use of normal prefixes creates some confusion, it is set off in
parentheses and the second set of prefixes is used.

2 di bis
3 tri tris
4 tetra tetrakis
5 penta pentakis
6 hexa hexakis
7 hepta heptakis

Examples:
+
CoCl2 ( NH2CH2CH2NH2 )  dichloridobis(ethane-1,2-diamine)cobalt(III).
 2

NiCl2 ( PPh3 )2  , dichloridobis(triphenylphosphine)nickel(II).

 
(vi) Oxidation state of the metal in cation, anion or neutral coordination entity is indicated by
Roman numeral in the parentheses after the name of metal.

(vii) If the complex ion is a cation, the metal is named same as the element. For example, Co
in a complex cation is called cobalt and Pt is called platinum. If the complex ion is an anion,
the name of the metal ends with the suffix-ate. For example, Co in a complex anion,
[Co(SCN)4]2– is called cobaltate. For some metals, the Latin names are used in the complex
anions.
iron (Fe) ferrate
lead (Pb) plumbate
silver (Ag) argentate
 tin (Sn) stannate
gold (Au) aurate

+
Examples ; Co(NH3 )4 Cl2  , tetraamminechloridocobalt(III).
(NH4 )2 Co(SCN)4  , ammonium tetrathiocyanato-S-cobaltate(II).
(viii) The neutral complex molecule is named similar to that of the complex cation.
Example ; [CrCl3(py)3], trichloridotris(pyridine)chromium(III).

(ix) The prefixes cis- and trans- designate adjacent and opposite geometric locations.
For examples,
[Pt(NH3)2Cl2], cis- and trans-diamminedichloridoplatinum(II),
[CoCl2(NH3)4]+, cis- and trans-tetraamminedichloridocobalt(III).

(x) If there is any water of crystallization, it is to included in the name. For example,
Cr(H2O)4 Cl2 Cl.2H2O :
tetraaquadichlorido chromium(III) chloride-2-water or
tetraaquadichlorido chromium(III) chloride dihydrate.

Effective Atomic Number Rule given by Sidgwick:

Effective Atomic Number (EAN) = Atomic no. of central metal – Oxidation state of
central metal + No. of electrons donated by ligands.

Valance field theory:

The summarise points of valance field theory are

(I) Central atom loses a requisite number of electron to form the ion

29 Cu : [Ar]3d10 4s1
2+
29 Cu : [Ar]3d9 4s0

(II) Central metal ion hybridizes their empty orbital to acquire the lone pair electrons from
ligand.

(III) Lone pair electrons from ligands are accepted in these empty hybrid orbitals

(IV) Vacant hybrid orbitals of ion overlap with the orbitals containing lone pair and form
ligand ⎯⎯
→ metal,  bond. This bond is also called ligand metal coordinate bond.
 hybri Type of complex Geometry Type of d
disati orbital
on
1 sp Linear –
2 sp2 Trigonal planar –
3 sp3 Tetrahedral –
4 2 Inner complex or low Square planar d x2 − y2
dsp
spin complex
5 sp3d Outer complex or high Trigonal biplanar dZ2
spin complex
6 dsp3 Inner complex or low Square planar d x2 − y2
spin complex
7 sp3d2 Outer complex or high Octahedral d x2 − y2 and
spin complex
dZ2
8 d2sp3 Inner complex or low Octahedral d x2 − y2 and
spin complex
dZ2

Complex O.S HBZ Geometry Unpaired Magnetic

‘e’ property
[NiCl4 ]2− +2 sp3 Tetrahadral 2 Paramagnetic
[Ni(CN)4 ]2− +2 dsp2 Square 0 Diamagnetic
planar
[Ni(CO)4 ] 0 sp3 Tetrahadral 0 Diamagnetic
2+ +2 3 2 Octahedral 2 Paramagnetic
[Ni(NH3 )6 ] sp d
[Mn(CN)6 ]4 − +2 d2sp3 Octahedral 1 Paramagnetic
[MnCl4 ]2− +2 sp3 Tetrahadral 5 Paramagnetic
[CuCl4 ]2− +2 sp3 Tetrahadral 1 Paramagnetic
[Cu(NH3 )4 ]2+ +2 dsp2 Square 1 Paramagnetic
Shifting of e planar
3d → 4p
[Cr(NH3 )6 ]3+ +3 d2sp3 Octahedral 3 Paramagnetic
[Cr(H2O)6 ]3+ +3 sp3d2 Octahedral 3 Paramagnetic
[Fe(CN)6 ]4 − +2 d2sp3 Octahedral 0 Diamagnetic
[Co(NH3 )6 ]3+ +3 d2sp3 Octahedral 0 Diamagnetic
[CoF6 ]3− +3 sp3d2 Octahedral 4 Paramagnetic
Limitation of valance field theory
The valence bond theory was fairly successful in explaining the geometry and magnetic
properties of complexes number of limitations

(I) The theory does not offer any explanation that why most of the complexes are coloured

(II) Sometimes the same metal ion assumes different geometry when formation of complex
and takes place. This theory is unable to explain why at one time the electron are rearranged
against hund’s rule while at at other time the electronic configuration is not disturbed.

Example:

[Co(NH3 )6 ]3+ :

3d 4s

Co: [Ar]3d7 4s2 :

3d 4s

Co3+ : [Ar]3d6 4s0 :

3d 4s

[Co(NH3 )6 ]3+ Intermediate stage:

3d 4s 4p

Hund rule violated

[CoF6 ]3− :

3d 4s

Co: [Ar]3d7 4s2 :

3d 4s

Co3+ : [Ar]3d6 4s0 :

3d 4s

[CoF6 ]3+ Intermediate stage:

 3d 4s 4p 4d

Hund rule not violated

(III) In the formation of [Cu(NH3 )4 ]2+ ,one electron is shifted from 3d to 4p orbital.The theory
is silent about the energy availibality for shifting auch an electron.

(IV) It does not explain why magnetic moment varies with temperature.

Q: Why hybridization like dsp3d does not exist?

Crystal field theory

In crystal field theory no such case of hybridization or co-ordinate bond. Crystal field theory
focused only the following two points

(I) It assumes that the attraction between the central metal ion and the ligand is purely
electrostatic.

(II) When ligand surround the central metal ion, the electrons on the central metal are under
repulsive force from those on ligands, due to this electron, occupy the d orbitals from the
furthest away from the direction of approach of ligand (resulting splitting of ‘d’ orbital)

Note: This theory fails to explain the formation of coordination sphere in which central
metal is

in zero oxidation state ex. Ni(CO)4 ,Fe(CO)5 etc.

 eg (d x2 y2 ,dz2 )

t2g (d xy ,d yz , dzx )

Formation of octahedral complex:

In an octahedral complex, the metal is at the center of octahedron and the ligands are at six
corners of octahedron.

The direction x, y and z points to three adjacent corners of the octahedron. The lobes of the
eg orbitals ( d x2 − y2 anddz2 ) point along the axes x, y and z and the lobes of the t 2g orbitals (
d xy ,d yz ,dzx ) point in between the axes.

It follows the approaches of sox ligand along the x , y, z,–x,–y and –z direction, which cause a
very strong repulsion from ligands that’s why it increase the energy of d x2 − y2 anddz2 orbitals.
Thus under the influence of an octahedral ligand the‘d’ orbital split into two groups of
different energies.
 eg (d x2y 2 ,d z2 )

0.6

Energy
Bary centre (metal ion 'd' orbital)
0.4
t 2g (d xy ,d yz , dzx )

(metal 'd' orbital)

The weighted means that the algebraic sum of energies of 3 orbitals of t 2g and energies of 2
orbitals of eg should be zero.

(Note: eg : exempli gratia, t 2g :triply gerade (denerate) orbitals, these names only have
scientific meanings)

So more the spilliting more the chance that ‘d’ electrons will acquire the lower energy
splitted ‘d’ orbitals.

Spectrochemical series:
Weak field ligand
I−  Br −  S2−  Cl −  NO3−  F −  OH−  EtOH  Oxalate  H2O  NCS− (n bonded)
 EDTA  NH3  pyridine  ethylenediammine  dipyridyl  o − phenanthroline
 NO2−  CN−  CO
Strong field ligand

In general:

Halogen donor< Oxygen donor < Nitrogen donor < Carbon donor

Such a series is termed as spectrochemical series. It is an experimentally determined series

based on the absorption of light by complexes with different ligands.

For d4 configuration, the fourth electron will singly occupy eg orbital (according to Hund’s
rule) or will undergo pairing in t 2g orbital, which of these possibilities occurs, depends on
the relative magnitude of the crystal field splitting,   and the pairing energy, P
P: P represents the energy required for electron pairing in a single orbital , P is constant for a
metal irrespective of ligand.

The two possibilities are:

(i) If   < P, the fourth electron enters one of the eg orbitals giving the configuration t 32g eg1 .
Ligands for which   < P are known as weak field ligands and form high spin complexes.

(ii) If   > P, it becomes more energetically favourable for the fourth electron to occupy a t2g
orbital with configuration t 42g eg0 . Ligands which produce this effect are known as strong
field ligands and form low spin complexes.

Factor For crystal field splitting:

Crystal field splitting (   ) is the result of repulsion between orbitals and central metals. It
depends on

(I) Stronger the ligand field greater the splitting.

(II) Higher the charge on central metal greater the splitting.   for M3+ complex are roughly
50% larger than the value for M2+ complexes.

(III) Whether the element is in the first, second or third row of transition element. The value
of   increases by about 30% between adjacent member down a group a transition element.

Crystal field stabilization energy:

Formula: CFSE = – 0.4 (n) t 2g + 0.6(n')eg    + n *P

n : number of electron(s) in t 2g

n’ : number of electron(s) in eg

  : crystal field splitting energy for octahedral complex

n* : number of extra electron pairs formed because of the ligands in comparison to normal
degenerate configuration.

Formation of tetrahedral complex:

In tetrahedral coordination entity formation, the d orbital splitting is inverted and is smaller
as compared to the octahedral field splitting. For the same metal, the same ligands and
4
metal-ligand distances, it can be shown that   (t) =     (O) . This may attribute to the
9
following two reasons.

(i) There are only four ligands instead of six, so the ligand field is only two thirds the size; as
the ligand field spliting is also the two thirds the size and

(ii) the direction of the orbitals does not concide with the direction of the ligands. This
reduces the crystal field splitting by roughly further two third. So

 2  2 4
  (t) =        (O) =     (O)
3 3 9

Consequently, the orbital splitting energies are not sufficiently large for forcing pairing and,
therefore, low spin configurations are rarely observed.

Note: CFSE is zero for d0 ,d5 ,and d10 arrangement for both octahedral or tetrahedral
complexes. For all other arrangement   (O) is always greater than   (t) .It follows that
octahedral complexes are generally more stable and more common than tetrahedral
complexes.

Despite this some tetrahedral complexes are formed and are stable. Tetrahedral complex are
favoured :

1. Where the ligands are large and bulky and could cause crowding in an

octahedral complex.

2. Where attainment of a regular shape is important. For tetrahedral

structures d0, d2, d5, d7 and d10 configurations are regular. Some tetrahedral complexes which
are regular are:

TiIVCl4 :(e0g ,t 2g
0
)
[Mn VIIO4 ]− :(e0g ,t 02g )
[FeIIICl4 ]− :(e2g ,t 32g )
[ZnIICl4 ]2− :(eg4 ,t 2g
6
)

3. When the ligands are weak field, and the loss in CFSE is thus less important,
4. where the central metal has a low oxidation state. This reduces the magnitude of  

5. where the electronic configuration of the central metal is d0 , d5, and d10 as there is ho
CFSE.

6. Where the loss of CFSE is small, e.g. d1 and d6 where the loss in CFSE is 0.13   or d2 and d7
where the loss is 0.27   .

6. Many transition metal chlorides, bromides and iodides form tetrahedral structures.

t 2g (dxy ,dyz , dzx )

0.4
Energy

Bary centre (metal ion 'd' orbital)

0.6

eg (dx2 y 2 ,dz2 )

(metal 'd' orbital)

Crystal field stabilization energy in tetrahedral complex:

Formula : CFSE = – 0.6 (n) eg + 0.4(n')t 2g    + n *P

As the   (t) is always smaller than   (O) while P is same, thus it is never energetically
favourable to pair electrons and tetrahedral complex all are high spin .So CFSE becomes

CFSE = – 0.6 (n) eg + 0.4(n')t 2g   

Theory of colour in complex compound:

Complementary colour : Complementary colors are pairs of colors which, when combined
or mixed, cancel each other out (lose hue) by producing a grayscale color like white or black.
When placed next to each other, they create the strongest contrast for those two colors.
Complementary colors may also be called "opposite colors."
 Violet &
Indigo
Red

Blue
Orange

Green
Yellow

Complex compounds absorb the light of a particular energy and generate a d-d transition,
and the complementary colour is given by the complex compounds.

Visible sunlight light spectra:

 1 
That’s why although the scattering of light   4  ,but the colour of sky id blue rather than
 
indigo.

Compound Comment Light Colour of complex

absorbed compound
(Complementary colour)
[CoIII (CN)6 ]3− large splitting due Blue Orange
to strong field
ligand
[CoIIIF6 ]3− small splitting due Red Green
to weak field ligand

[CrIII (NH3 )6 ]3+ large splitting due Violet-indigo Yellow

to strong field
ligand
[CrIII (H2O)6 ]3+ small splitting due Yellow deep violet
to weak field ligand

Cases when complex compound are colourless:

In general, two cases:

(I) In complex there is no possibility of d-d transition like if all ‘d’ orbitals are empty like
Sc3+ or Ti4 + complexes or ‘d’ orbitals are completely filled like Zn2+ complexes.

(II) Either complex absorb light in infrared light then the complementary color will not be in
visible light or the complex absorb light in ultraviolet then complementary colour will not be
in visible light. In both cases the complex will be colorless.

Colour due to charge transfer: Potassium

permanganate is purple in colour due to LMCT (Ligand to metal
charge transfer) rather than d-d transition as Mn in KMnO4 exist
with +7 oxidation state and it has no d electrons (
Mn +7 :3d0 4s0 ). In the charge transfer within the molecule,
photons promote an electron from the highest energy MO orbital
from one of the ligand (O2− ) to an empty d orbital of Mn. Causing a reduction in the
oxidation state of Mn from +7 to +6 momenteraly. This promotion is equivalent to the energy
of a yellow photon, so yellow light is absorbed and make us to see as its complementary
colour purple. The colour is due to [MnO4 ]− so either KMnO4 or NaMnO4 all are purple.

Same explanation for the orange red colour of K 2Cr2O7

Oxidation state of Fe and colour in [Fe(H2O)5 NO]2+ : There have been other theories that
the odd electron of NO keeps oscillating between the central ion and ligand NO and thus, the
oxidation state of the central ion should oscillate between +I and +II. Many state this as the
reason for the intense brown colour of the compound, referring to the colour producing
effect known as ‘Charge transfer’.
Note: asked ones in IIT-JEE , answer given was +1.

NO is often acts as a three electron donor, in contrast to most ligands which donates two
electrons. Thus three CO groups may be replaced by two NO groups
[Fe(CO)5 ] + 2NO ⎯⎯
→[Fe(CO)2(NO)2 ] + 3CO
[Co(CO)6 ] + 4NO ⎯⎯
→[Cr(NO)4 ] + 6CO

Q. Suggest a reason why Fe(CO)5 is colourless while Fe(bipy)(CO)3 is intensely purple

in colour.
The intense colour of the latter complex is strongly suggestive of a charge transfer transition
and since the metal is already fully reduced (zero oxidation state), it is highly
likely that this involves a MLCT (Metal to ligand charge transfer) transition. The π* levels of
the bipy or CO ligands are possible acceptors but the fact that Fe(CO)5 doesn’t show this
colour suggests that it is the bipy π* levels that are involved in Fe(bipy)(CO)3. Since there
should be MLCT transitions to the CO π* levels as well, we assume that the lack of colour for
Fe(CO)5 means that these transitions fall in the UV rather than the visible.
3− 3−
Q: The complex FeF6  does not have any color while CoF6  has green colour. Why?
While from theory in both the complexes d-d transition is possible.
3−
Ans: In CoF6  it absorb red colour light so it shows complementary colour green , while in
3−
the case of FeF6  the is a very weak splitting so the light absorbed will be in infrared
region so its complementary colour is not in visible region of light so it appears colourless.

1. Both Fe(CN)64− and Fe(H2O)62+ appear colourless in dilute solutions. Consider the
following statements. Which is/are correct?
(A*)The former ion is low spin and latter is high spin
(B*)Former has zero unpaired electrons while latter has 4 unpaired electrons
(C*)   for Fe(CN)64− is so large that the absorption peak is in ultraviolet region
(D*)   for Fe(H2O)62+ is so small that the absorption peak is in infrared region

2. A solution of [Ni(H2O)6]2+ is green, but a solution of [Ni(CN)4]2- is colourless because

(A*) The value of   for the H2O complex is in the visible region
(B*) The value of   for the CN− is in the ultraviolet region
(C) H2O is a strong field ligand
(D*)CN− is a strong field ligand

3+ 3+
3. A complex CoA6  is red coloured while CoB6  is green coloured. Then which of the
following is/are correct
(A*) Ligand B produce smaller crystal field splitting than A
(B) Ligand A produce smaller crystal field splitting than B
(C) [CoA6]3+ can be oxidise more easily
(D*) [CoB6]3+ can be oxidise more easily

Limitations of crystal field theory:

(1) It considers only the metal ion d-orbitals and gives no consideration at all to other metal
orbitals (such as s, px, py and pz orbitals).

(2) It is unable to account satisfactorily for the relative strengths of ligands. For example it
gives no explanation as to why H2O is a stronger ligand than OH– in the spectrochemical
series.

(3) According to this theory, the bond between the metal and ligands are purely ionic. It
gives no account on the partly covalent nature of the metal ligand bonds. It does not explain
the bonding of complex having neutral metal like Ni(CO)4 ,Fe(CO)5 etc

(4) The CFT cannot account for the  -bonding in complexes.

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Stability of complex cpmpound:

Some important generalisation regarding stability constants:

(ii) For a given metal and ligand the stability is generally greater when the charge on the
metal ion is greater. Thus, stability of coordination entities of ions of charge 3+ is greater
than the entities of 2+ ions.

(iii) Further, for the divalent ions of the first-row transition elements, irrespective of the
ligand involved, the stabilities vary in the Irving-Williams order:

MnII  FeII  CoII  NiII  CuII  ZnII

This order was found to hold for a wide variety of ligands. There are three strands to the
explanation of the series.

1. The ionic radius is expected to decrease regularly for Mn2+ to Zn2+. This would be the
normal periodic trend and would account for the general increase in stability.

2. The crystal field stabilisation energy (CFSE) increases from zero for manganese(II) to a
maximum at nickel(II). This makes the complexes increasingly stable. CFSE returns to zero
for zinc(II).

3. Although the CFSE for copper(II) is less than for nickel(II), octahedral copper(II)
complexes are subject to the Jahn–Teller effect which results in a complex having extra
stability.

(IV)In F¯, Cl¯, Br¯, I¯ ;F¯ forms strongest complexes due to small size & hence high charge
density.

(v) (a) The stability also depends on the formation of chelate rings. If L is an unidentate
ligand and L–L, a didentate ligand and if the donor atoms of L and L–L are the same element,
then L–L will replace L. The stabilisation due to chelation is called the chelate effect. It is of
great importance in biological systems and analytical chemistry.

(b) If a multidentate ligand happens to be cyclic and there are no unfavourable steric effects,
a further increase in stability occurs. This is termed the macrocyclic effect.

(VI) Octahedral complexes are generally more stable and more common than tetrahedral
complexes.

Crystal field splitting

 Name Shape Energy diagram

1 Octahedral

2. Tetrahedral

3. Square planar

Squire
4.
pyrimidal
 Trigonal
5.
bipyramidal

Electronic configuration:

Cr: [Ar] 3d5 4s¹

Cu: [Ar] 3d10 4s¹

Pd: [Kr] 4d¹⁰

Pt:  Xe 4f 14 5d9 6s1

Au:  Xe 4f 14 5d10 6s1

Some important points:

1. Pt usually form square planar complex: Platinum has bigger d orbitals than nickel does,
which can hold more electron density more capably, because the electron density can be
more spread out in a larger d orbital. Therefore, platinum can support a higher-energy
structure such as the square planar structure.

2. Square Planar Complexes. In square planar molecular geometry, a central atom is

surrounded by constituent atoms, which form the corners of a square on the same plane.
The geometry is prevalent for transition metal complexes with d8 configuration. This
includes Rh(I), Ir(I), Pd(II), Pt(II), and Au(III). The reason that many d8 complexes are
square-planar is the very large amount of crystal field stabilization that this geometry
produces with this number of electrons.

Square planar complexes are formed by d8 ions with strong field ligands for example
[NIII (CN)4 ]2− . The crystal field splitting   larger for second and third row transition
elements, and for more highly charged species All the complexes of Pt(+II) and Au(+lll) are
square planar including with weak field such as halide ions.
John teller distortion:

The two eg orbitals d x2 − y2 and dZ2 are normally degenerate. However, if they are
asymmetrically filled then this degeneracy is destroyed, and the two orbitals are no longer
equal in energy.

Asymmetrical electronic arrangements:

Electronic t 2g eg Nature of ligand Example

configuration field

d4 Weak field Cr(+II),

(high spin Mn(+III)
complex)

d7 Strong field Co(+II),

(low spin Ni(+III)
complex)

d9 Either strong or Cu(+II)

weak

If the dZ2 orbital contains one more electron than the d x2 − y2 orbital then the ligands
approaching along +Z and -Z will encounter greater repulsion than the other four ligands.
The repulsion and distortion result In elongation of the octahedron along the axis. This is
called tetragonal distortion. Strictly it should be called tetragonal elongation. This form of
distortions commonly observed.

If the d x2 − y2 orbital contains the extra electron, then elongation will occur along the x and y
axes This means that the ligands approach more closely along the z axis. Thus, there will be
four long bonds and two short bonds . This is equivalent to compressing the octahedron
along the Z axis and is called Tetragonal compression. Tetragonal elongation is much more
common than tetragonal compression and it is not possible to predict which will occur.

Isomerism:

Isomerism in coordination compounds may be divided into two types:

1. Structural isomerism:

(a) Ionisation isomerism

(b) Hydrate isomerism

(c) Coordination isomerism

(d) linkage isomerism

(e) Polymerisation isomerism

(f) Coordination isomerism

2. Stereoisomerism:
(I) geometrical isomerism:

(II) Optical isomerism:

1. Structural isomerism: It is displayed by compounds that have different ligands within

their coordination sphere.

(a) Ionisation isomerism: This type of isomerism arises when coordination compounds
give different ions in solution, Example: there is two isomers of Co(NH3 )5 BrSO4

[Co(NH3 )5 Br]SO4 [Co(NH3 )5 Br]2+ + SO42−

This isomer gives a white ppt. of BaSO4 with BaCl2 solution.

[Co(NH3 )5 SO4 ]Br [Co(NH3 )5 SO4 ]+ + Br −

This isomer gives a Yellow ppt. of AgBr with AgNO3 solution.

(b) Hydrate isomerism: This type of isomerism arises when different number of water
molecule are present inside and outside of the coordination sphere.

Note: This type of isomerism arises when different number of NH3 or other neutral molecule
are present inside and outside of the coordination sphere.

Complex are generally dissolved in water so water crystallization is taken into account.

CrCl3 .6H2O shows three isomers.

(i) [Cr(H2O)6 ]Cl3 :Violet colour

(ii) [Cr(H2O)5 Cl]Cl2 .H2O : Green colour

(iii) [Cr(H2O)4 Cl2 ]Cl.2H2O : Green colour

Order of conductivity:

[Cr(H2O)6 ]Cl3 > [Cr(H2O)5 Cl]Cl2 .H2O > [Cr(H2O)4 Cl2 ]Cl.2H2O

(c) Coordination isomerism: This type of isomerism is observed in coordination

compounds having both cationic and anionic ions. The ligands (all or some) are interchanged
in both the cationic and anionic ions to form isomers

[Pt(NH3 )4 ][CuCl4 ] and [Cu(NH3 )4 ][PtCl 4 ]

We write [Cu(NH3 )4 ] first because due to interchange of cation this part is now cationic while
[PtCl 4 ] is anion.

[Cr(NH3 )4 (SCN)2 ][Cr(NH3 )2(SCN)4 ]

(d) Linkage isomerism: This type of isomerism occurs in complex compounds which
contain ambidentate ligands like NO2− , SCN− , CN− ,CO etc.

[Co(NH3 )5 NO2 ]Cl2 and [Co(NH3 )5 ONO]Cl2

(e) Polymerisation isomerism: This type of isomerism exists in compounds having same
stoichiometric composition but different molecular compositions. The molecular
compositions are simple multiples of simplest stoichiometric arrangement.

[Pt(NH3 )2 Cl2 ] and [Pt(NH3 )4 ][PtCl4 ] and [Pt(NH3 )3 Cl]2[PtCl4 ]

(f) Coordination isomerism: This type of isomerism is exhibited by polynuclear complexes

by changing the position of ligands with respect to different metal atoms present in the
complex.
2+ 2+

NH2 NH2
(NH3)4 Co Cr (NH3)2 Cl2 (NH3)3ClCo Cr (NH3)3 Cl
O2 O2
and

2. Stereoisomerism: Compounds are stereoisomer when they contain the same ligand in
their coordination sphere but differ in the way that these ligands are arranged in space.

(I) geometrical isomerism: This isomerism is due to ligands occupying different position
around the central metal atom/ion. This type of isomerism is also known as cis-trans
isomerism.

Square planar complex:

(a) Ma2b2 type complex: a and b are monodentate ligand

b b b a

M M

a a a b

Cis Trans
 NH 3 NH3 Cl
NH 3

Pt Pt

Cl NH 3
Cl Cl

Cis Trans

(b) Ma2bc type complex: a , b and c are monodentate ligand

b c b a

M M

a a a c

Cis Trans

NH 3 NH3 Cl
NO2

Pt Pt

Cl Cl Cl NO2

Cis Trans

(c) Mabcd type complex: a, b, c and d are monodentate ligand

c b c a d a
M M M
b b c
d a d

(c) MA 2 type complex: A is unsymmetrical bidentate ligand

Ex: [Pt(Gly)2 ]
 NH 2 NH2
CH 2 CH 2
Pt
CO CO
O- O-
Cis

NH 2 O-
CH 2 CO
Pt
CH 2
CO
O- NH2
Trans
Octahedral complexes:

(II) Optical isomerism:

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