Co - ordination Compounds

Co-ordination Compounds
Syllabus
Introduction to co-ordination compounds, Werner's theory, Ligands, Co-ordination number, Denticity, Chelation,
IUPAC nomenclature of mononuclear co-ordination compounds, Isomerism, Bonding Valence bond approach
and basic ideas of Crystal field theory, Colour and magnetic properties, importance of co-ordination
compounds (in qualitative analysis, extraction of metals and in biological systems).

Different types of salt are formed due to addition of molecular compounds.

1. Double salts : Double salts are those molecular compounds which exists only in crystal lattice
but lose their identity in solution.
e.g., KCl. MgCl2.6H2O  K+ + Mg+2 + 3Cl– + 6H2O.
Double salts when dissolved in water ionise.
2. Complex salts : Complex salts are those molecular compounds which retain their identity in solid
/ crystal lattice as well as in the solution.
e.g., Potassium ferrocyanide is a complex compound which is formed by adding KCN to a
saturated solution of ferrous cyanide
4KCN + Fe(CN)2 – K4[Fe(CN)6]
K4Fe(CN)6 is dissolved in water, the resulting solution does not give positive tests for ferrous or
cyanide ions but we get a positive test for [Fe(CN)6]4 –.
A complex ion exists as a single entity and is generally enclosed in square brakets [ ].
Complex ion:
A complex ion may be difined as an electrically charged radical formed by the combination of a simple
cation with one or more simple molecules, negative ions or positive ions also. For example,
[Cu(NH3)4]2+ ion is a complex ion formed of Cu++ ion and neutral ammonia molecules.
[Fe(CN)6]4– is composed of ferrous ion (Fe2+) and negative CN– ions.
Central metal atom or ion: The metal atom or ion with which netrual molecules or negative ions or
sometimes positive ions are linked in a complex ion, is called central atom or ion. for example, in the
complex ion [Pt(NH3)4Br2]++, platinum is the central metal ion.
Co-ordination compounds: In a comploex ion, the central metal ion is surrounded by a number of
negative ions or the neutral molecules (known as ligands) which are linked by co-ordinate or dative
bonds. Therefore, the complex compounds are often called co-ordination compounds.
Co-ordination number (C.N.) : The total number of monovalent (monodentate) ligands or the total
number of donor atoms co-ordinated to the central metal atom or ion in a complex, is called co-
ordination number of the central metal ion or atom.
For example, in the complex, K3[Al(C2O4)3], the co-ordination number of aluminium ion is six because
there are six donor oxygen atoms of three oxalate ions co-ordinated to aluminium ion.
Co-ordination sphere: The central atom or ion along with the co-ordinated ligand ions or molecules in
a complex ion, are enclosed in square brackets [ ]; it is collectively called co-ordination sphere. For

XII - Chemistry 31
 Co - ordination Compounds

example in the complex [CO(NH3)5Br]SO4, the five ammonia molecules and one bromide are co-
ordinated to central cobalt ion. They are in the co-ordination sphere.
 Ions or molecules in the co-ordination sphere are not ionized in solution. For example in the above
complex ion, bromide (Br–) ion is not ionized in solution. Only sulphate ion SO42– can be tested.
Charge on the complex ion: The magnitude of charge present on a complex ion is the algebraic
sum of the charges carried by the central metal ion and the ligands bonded to it. For example,
the complex ion [Fe(CN)6]4– carries a charge of –4because the central ferrous ion has + 2 charge
and the six ligand molecules, i.e., 6CN– ions carry a total charge of –6. Thus the total charge on
the complex ion it (+2)+ (–6) = –4.
Ligand:
Any ion or molecule havng at least one atom with a lone pair of electrons qualifies as a ligand. This
atom having a lone pair acts like a donor atom or donor site.
Types of ligand: Depending upon the number of donor atoms or sites, ligands may be classififed into
various categores.
(a) Unidentate or Monodentate ligands: They can donate only one pair of electrons to the central
metal atom or ion. Thus, they are attached with the central metal atom or ion only at one point.
Such ligands are known as uni or monodentate ligands. For example:
F–, Cl–, NH3, CO, NO, CN–, I–, Br–, OH–, H2O, NO2–, C5H5N(Pyridine), etc.
(b) Bidentate ligands: Ligands which have two donor atoms and therefore tend to attach to the
central ion at two sites are called bidentate ligands.
For example,
OH

H2 CH 3  C  N :
O  C  O CH 2  N :

CH 2  NH 2
 CH 3  C  N :
O CO 
CH 2  NH
Oxalate ion 2
COO 
Ethylene diammine OH Glycinate ion
 Ox   en  Dimethyl glyoxime
 DMG 
(c) Polydentate ligands: Molecules in which there are more than two donor atoms or sites are called
polydentate ligands. Those polydentate ligands with three, four or six donor sites are called
tridentate, tetradentate, pentadentate or hexadentate ligands respectively.
Ethylene diammine tetra acetate ion (EDTA ion) is an important example of hexadentate ligand.
It contains two nitrogen and four oxygen atoms as donor atoms.

OOCH 2C CH 2 COO
  CH CH  N
N 
2 2

OOCH 2C CH 2 COO

32 XII - Chemistry
Co - ordination Compounds

Chelating ligands:
Bidentate or polydenate ligands are attached by two or more donor atoms to the same central metal
ion giving a ring structure to the complex ion. Such ligands are called chelating ligands. The resulting
complex is called a chelate.
For example, complex formed by cupric ion and ethylene diammine (bidentate ligand) is a chelate.
Similarly, the complex [Al(C 2O4)3]3– is a chelate. Chelate (ring) complexes are more stable than
ordinary complexes having monodentate ligands. this increased stability of a ring complex formed due
to chelation is known as chelate effect.

CO-ORDINATION COMPOUNDS
Coordination compound may be defined as a compound that results from the combination of apparently
saturated molecules of different species and retain its identity in the solids as well as in dissolved state.
Preparation of Co-ordination Compounds:
These are generally prepard by substitution reactions, redox reactions and by direct combination of
the reactants. Thus, an aqueous solution of copper sulphate gives deep blue complex [Cu(NH3)4]++
in the presence of excess of ammonia. In this reaction, the ligand water molecules around copper ion
are replaced by ammonia.

[Cu(H 2 O) 4 ]SO 4  4NH 3  [Cu(NH 3 ) 4 ]SO 4  4H 2 O

Blue solution Deep blue complex

Metal ammines can be made by direct addition of a metal salt of liquid ammonia.

NiCl 2  6NH3  [Ni(NH 3 ) 6 ]Cl 2

Salt Liquid
ammonia

Addition of PtCl2 to ethylene diammine forms [Pt(en) 2 ]Cl 2 .

Cobalt nitrate when treated with conc. aquesous ammonia and NH 4 NO3 in the presence of hydrogen
peroxide gives nitrato pentammine cobalt (III) nitrate.

2[Co(H 2 O)6 ](NO3 )2  8NH 3  2NH 4 NO3  H 2 O2  2[Co(NO3 )(NH3 ) 5 ](NO3 ) 2  14H 2 O

Some Important Points :

1. The total number of ligands attached to a central ion is said to be the co-ordination number of
that ion. Thus co-ordination number (C.N.) of Ni2+ in [Ni(NH3)6]Cl2 is 6. Ag+ in [Ag(CN)2]– is
2.
2. The molecules or ions bonded directly to the central ion constitute what is often termed as co-
ordination sphere, written with square brackets.
3. One more important point is the oxidation state of central metal ion. It is the charge carried by a
complex ion and is the algebric sum of charges carried by central ion & the ligands co-ordinated to
it.

TYPES OF COMPLEX IONS

The complex ions can be grouped into three classes depending upon the nature of charge they
carry :

XII - Chemistry 33
 Co - ordination Compounds

1. Complex cation : A complex ion that has a net positive charge is called a complex cation, e.g.,
tetraamminecopper (II), [Cu(NH3)4]2+.
2. Complex anion : A complex ion that has a net negative charge is called a complex anion, e.g.,
hexacyanoferrate (II), [Fe(CN)6]–4.
3. Neutral Complex : A complex that has no net charge is called a neutral complex, e.g.,
hexacarbonyl chromium(0), [Cr(CO)6].
IUPAC Nomenclature of complex compounds
In order to name these compounds certain rules have been suggested by IUPAC.
1. The positive part of a coordination compound is named first and is followed by the negative
part.
2. The ligands are named first followed by the central metal. The prefixes di- tri-, tetra- etc,
are used to indicate the number of each kind of ligand present. The prefixes bis (two
ligands) tris (three ligands) etc. are used when the polydentate ligands surround the
central atom.
3. The ligands are named in alphabetical order. Names of the anionic ligands end in O, those
of cationic in ium. Neutral ligands have their regular names except that H 2O is named aqua;
NH3 ammine; NO nitrosyl; and CO carbonyl.
(a) Anionic Ligand Name
Fluoride (F -) Fluoro
Chloride (Cl-) Chloro
Bromide (Br -) Bromo
Iodide [I-] Iodo
Cyanide (CN-) Cyano
Hydroxide (OH-) Hydroxo
Oxide (O--) Oxo

Sulphate SO 24 Sulphato

Oxalate C 2 O4 2  Oxalato

Thiocyanate SCN- Thiocyanato

Nitrite O-–N=O Nitrito

Sulphite SO3 2 Sulphito

(b) Neutral ligands Name

Ammonia, NH3 Amine
Water, H2 O Aquo
Carbon monoxide, CO Carbonyl
Nitric oxide, NO Nitrosyl

34 XII - Chemistry
Co - ordination Compounds

(c) Cationic Ligand Name

NO + Nitrosonium
NO 2 + Nitronium

 NH 
NH Hydrazinium
2 3
4. The oxidation state of the central metal is indicated in roman numbers in a bracket.
5. When a complex species has negative charge, the name of the central metal ends in –ate.
For some elements, the name of ion is based on the latin name of the metal (For example,
argentate for silver).
6. A complex containing two or more metal ions is known as a polynuclear complex. The
ligands which are linked with the two metal atoms are called bridging groups. These groups
are separated from the rest of the complext by hyphens. The bridging groups are indicated
by putting the prefix  before their names. For example, the complex
H2
N

(NH3)4Co Co(NH3)4 (NO3)4

N
O2

is named as octa-ammine--amido--nitro di cobalt (III) nitrate.

Name of some of the Complexes
[Cr(H2O)4Cl2]Cl Tetraaquadichlorochromium (III) chloride.
[Co(en)2Cl2]Cl Dichlorobis (ethylenediamine)cobalt (III) chloride.
K4[Fe(CN)6 ] Potassium hexacyanoferrate(II).
Ni(CO)4 Tetracarbonyl nickel (O)
K[Ag(CN)2] Potassium dicyanoargentate (I)
K[BF 4] Potassium tetrafluoroborate (III)
K3[Fe(C 2O4)3] Potassium trioxalatoferrate (III)
[Mn(H2O)6]2+ Hexaaquamanganese(II) ion

[Ni(NH3)6]Cl2 Hexaamminenickel(II) chloride

[Co(NH3)3 (NO2)3] Triamminetrinitrocobalt (III)
[NiCl2(CH3NH2)2] Dichloro-bis-(methylamine) nickel(II)
[Co(NH3)4 (H2O)Br] (NO3)2 Tetraammine aquabromocobalt (III) nitrate
K2 [SiF6] Potassium hexafluorosilicate (IV)
Na 2[Fe(CN)5NOS] Sodium pentacyanonitrosylsulphidoferrate (III)

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 Co - ordination Compounds

K2[Ni(EDTA)] Potassium ethylenediaminetetracetatonickelate (II)

Cl Cl
(C6H5)3P
Pd Pd
P(C6H5)3
Cl Cl
chlorotriphenyl phosphine palladium (II)–dichloro chlorotriphenyl
phosphine palladium (II)
Fe4[Fe(CN))6]3 Iron hexacyanoferrate(II)
LiAlH4 Lithium tetrahydroaluminate (III)
[Pt(Py)4][PtCl4] Tetrapyridineplatinum(II)tetrachloroplatinate(II)
Na2[SiF6] Sodiumhexafluorosilicate(IV)

WERNER'S THEORY

Werner in 1893, put forward a theory, known as Werner's co-ordination theory. Some important
postulates of this theory are as below:
1. Each metal ion possesses two types of valency.
(i) Primary or principle or ionisable valencies.
(ii) Secondary or subsidary or non-ionisable valencies.
2. Primary valencies are satisfied by anions only. The number of primary valencies depends upon
the oxidation state of central metal. These are represented by dotted lines in between the central
metal atom and anion.
3. The secondary valencies are satisfied by the ions or the neutral electron pair donor molecules.
These are represented by solid lines.
4. The ions attached by secondary valencies do not ionise when the complex is dissolved in a solvent.
e.g., [Co(H2O)6]Cl3 [Co(NH3)4]Cl3

Cl Cl
H2O H2O H3N NH3
H2O Co H2O Co Cl
Cl
H2O Cl H2O H3N
Cl
NH3

Advantage of Werner's Theory:

(i) It satisfactorily accounts for the behaviour of co–ordination complexes which could not be
explained on the basis of electronic theory of valency.
(ii) If offers an explanation for isomerism in co–ordination compounds.
(iii) It also predicts the existence of isomers of the type which had not been observed earlier.

36 XII - Chemistry
Co - ordination Compounds

Defects of Werner's Theory:

(i) There is not theoretical justification for this theory because the electron and the noble gases which
constitute the basis for all types of bondings, were not known at that time when the theory was
proposed.
(ii) This theory does not offer any explanation for cause of various properties like colour,
paramagnetic character, etc., shown by a lot of co–ordination complexes.
The new theories which have been proposed for explaining the structure of co–ordination
compounds account for their geometry, colour and magnetic properties.
EFFECTIVE ATOMIC NUMBER
Transition metals forms coordination compounds very readily because they have vaccant 'd' orbitals
which can accommodate electron pairs donated by ligand. Metal ion in the complex tends to attain
nearest stable inert gas configuration by gaining electrons from ligand.

Effective atomic number (EAN) of metal in a complex is given by :

EAN = Z–(O.N.) + 2(C.N.)

where Z = atomic number

O.N. = oxidation number

C.N. = coordination number

BONDING IN CO-ORDINATION COMPOUND

Valence Bond Theory

Important Features of Valence Bond Theory (VBT).

1. The central metal ion provides hybrid orbitals as required by the ligands i.e., coordination number
to form complex.

2. Each ligand should have at least one lone pair of electron.

3. The lone pair of electrons of the ligand overlap with empty hybrid orbital of metal ion.

4. If d-orbitals are involved in hybridisation that may be either inner viz (n – 1) d-orbital or the outer
viz (n) d-orbital. The complexes formed by these two ways are known as inner orbital and outer
orbital complexes respectively. Generally the inner orbital complexes are low spin and outer orbital
are high spin complexes.

5. If the complex is with one or more unpaired electron the complex is paramagnetic and if it does
not contain unpaired electron, it is diamagnetic.

1. Bonding in Hexaamminechromium(III) complex ion [Cr(NH 3)6]3+: Since the complex

ion is octahedral, the ligands (6NH 3 molecules) are bound to the central chromium (III) ion
through a set of d2sp3 hybrid orbitals. The outer electronic configuration of chromium is

XII - Chemistry 37
 Co - ordination Compounds

3d54s1 4p0 and that of Cr 3+ ion is 3d3 4s0 4p0. The Cr 3+ ion has two empty d-orbitals for
d2sp3 hybridization.
The presence of 3 unpaired electrons in the 3d - orbital accounts for the paramagnetic
nature of the complex.

Cr
5 1
3d 4s 3d 4s 4p

3+
Cr
3
3d 3d 4s 4p

[Cr(NH3)6]
3+ × × × × × ×
× × × × × ×
3d NH3 NH3 NH3 NH3 NH3 NH3

2 3
d sp -hybridisation

2. Bonding in hexacyanoferrate(II), [Fe(CN)6]4–: The cyanide ion, CN–, is a strong ligand and it
is assumed that the electrons in 3d-orbitals are redistributed under the influence of strong electric
field of cyanide ions to make available two empty 3d-orbitals for d2sp3 hybridization.

Fe
3d 4s 4p
2+
Fe
3d 4s 4p

[Fe(CN)6]
4– × × × × × ×
× × × × × ×
3d CN– CN– CN– CN– CN– CN–
Rearrangement
2 3
d sp – hybridisation

There are no unpaired electrons and this accounts for the diamagnetic nature of the complex.
3. Bonding in hexafluoroferrate (II), [FeF6]4–

Fe
6 2
3d 4s 3d 4s 4p 4d

2+
Fe
6 0
3d 4s 3d 4s 4p 4d

4–
[FeF6] × × × × × ×
× × × × × ×
– – – – – –
3d F F F F F F

3 2
sp d -hybridisation

38 XII - Chemistry
Co - ordination Compounds

As F– ion is weaker ligand so it will not involve 3d-orbitals but 4d-orbitals of Fe2+ ion. The
octahedral geometry of this complex is therefore explained by sp3d2 hybridization and not by d2
sp3 hybridization. Since 4d-orbitals are involved in complex formation, the complex is called an
outer-orbital complex. The presence of 4 unpaired electrons in 3d-orbitals account for the
paramagnetic nature of complex.
4. Bonding in tetracarbonylnickel(0), Ni(CO)4: The outer electronic configuration of nickel atom
is 3d8 4s2 4p0. The nickel in the complex should have empty s-orbital for sp3 hybridization.
Therefore, two 4s electrons are transferred to 3d-orbitals to make available one empty 4s-orbital.
The transfer of electrons into 3d-orbitals pair up all the electrons which accounts for its diamagnetic
behaviour.

Ni
3d 4s 4p

Ni in hybrid
orbital
3d 4s 4p

Ni(CO)4 × × × ×
× × × ×
3d CO CO CO CO

3
sp -hybridisation

DRAWBACKS OF VALENCE BOND THEORY

(a) This theory describes only qualitatively the type of bonding in co–ordination compounds.
(b) The optical absorption spectra and detailed magnetic properties of co-ordination complexes are not
explained by this theory.
Importance of Co-ordination Compounds:
(i) Animal and plant world:
Chlorophyll, the green coloured plant pigment, a photosensitizer, is the magnesium complex
with pyrrole nucleus in porphyrin unit. Haemoglobin is an iron complex. It is oxygen transporter
in the red blood corpuscles.
(ii) Hardness of water:
The hexadentate ligand, EDTA forms very stable complexes with various metal ions. This is
employed in the estimation of hardness of water by simple titration method.
(iii) The redox behaviour of metal ions"
The oxidation reduction of some metal ions is changed in the presence of certain ligands. For
example in the presence of ligands (such as NO2 ,CO3 ) cobalt is easily oxidised from +2 to
+3 oxidation state. A lot of enzymes containing metal ions (like Mo, Cu, Fe, etc.) make use of
this property in performing catalyzed biochemical reactions.
(iv) Electroplating of metals:

The cor-ordination compounds of silver Na  Ag  CN 2  and gold K  Au  CN 4  are used as

XII - Chemistry 39
 Co - ordination Compounds

electrolytes for electroplating of metals. These complexes release metal ions in a controlled
way for reduction at cathode.
(v) Extraction of metals:
The extraction of silver and gold from their ores by cyanide process involves the formation of
co–ordination complexes as follows:

2Na  Ag  CN 2   aq   Zn  Na 2  Zn  CN 4   aq   2Ag 

The complex nickel tetracarbonyl is used in the extraction and purification of nickel in Mond's
process
(vi) Detection and estimation of ions:

Cu 2  ,Fe3 and Zn 2 are detected as their complexes with ferrocyanide ion. Nickel is
detected and estimated as its red dimethyl glyoxime complex. Mg and Al are estimated as
their complexes with oxine (8–hydroxy quinoline).
(vii) In chemotherapy:
Cyanocobalamine (Vitamin B12) is a co-ordination compound of cobalt and is required for
treatment of pernicious anaemia, platinum complex cis  PtCl 2  NH 3 2  known as cis-platin
is used in treatment of cancer.
(viii) As catalysts:
Zeiglar–Natta catalyst, used for polymerization of olefins is a co-ordination complex of TiCl4
and R3Al. The Wilkinson's catalyst (Ph3P)3 RhCl is used for the hydrogenation of alkenes.

ISOMERISM
1. Structural Isomerism :
(a) Hydrate isomerism – Compounds which have same composition but differ in the number
of water molecule as ligands and as molecules of hydration are called hydrate isomers.
e.g., [Co(H2O)6]Cl3 & [Co(H2O)4Cl2]Cl.2H2O
(b) Ionisation Isomerism – Compounds which gives different ions in solution at though having
same composition are called ionization isomers.
e.g., [Co(NH3)5SO4]Br & [Co(NH3)5Br]SO4
(c) Linkage Isomerism – Occurs when more than one atom in a monodentate ligand functions
as a donor.
e.g., [Co(NH3)5NO2]Cl & [Co(NH3)5ONO]Cl
(d) Co-ordination Isomerism – This isomerism is possible when both positive and negative ions
of a salt are complex ion.
e.g., [Cr(NH3)6][Co(CN)6]
(e) Co-ordination position isomerism – This type of isomerism arises in the bridged
complexes due to difference in the attachment of ligands with the metal atom.

40 XII - Chemistry
Co - ordination Compounds

OH
e.g., (NH3)4Co Co(NH3)2Cl SO4
Cl

OH
and Cl(NH3)3Co Co(NH3)3Cl SO4
Cl
2. Stereo Isomerism
(a) Geometrical isomerism is common in square planar and octahedral complexes.
(i) Square planar complexes with general formula; [ M A 2X2] ±n, [MA2XY] ±n, [MABX 2]±n,
[MABXY]±n, [M(AB)2]±n show isomerism.
Example :

NH3 NH3
Cl Cl
Co Co
Cl NH3
NH3 Cl
Cis Trans
Note : MABCD shows 3 geometrical isomers.
Tetrahedral complexes do not show geometrical isomerism.
(b) Octahedral complexes with general formula, [MA4X2], [MA4XY], trans. [M(AA)2X2] shows
geometrical isomerism.

Cl Cl
NH3 Cl
NH3 NH3
(i) e.g., Co Co

NH3 NH3 NH3 NH3

Cl NH3
Trans-[Co(NH3)4Cl2] Cis-[Co(NH3)4Cl2]

Cl en
Cl
(ii) en Co en Co
Cl
Cl en
Trans-[Co(en)2Cl2] Cis-[Co(en)2Cl2]
(c) The complex with formula [MA3X3] show facial and meridonial isomerism.
A A
A A X
X
M M
A X X X [with respect to A ligand]
X A
Fac-[MA3X3] Mer-[MA3X3]

Note : Complex with general formula [MABCDEF] shows 15 special geometrical isomers.

XII - Chemistry 41
 Co - ordination Compounds

2. Optical Isomerism
(a) Tetrahedral complexes with formula MABCD or M(AB)2 show optical isomerism
(b) Octahedral complexes having formula [MA2B2C2]± n, (MABCDEF), M(A–A)3, M(AA)2B2;
M(AA)B2C2 containing symmetrial bidentate ligand will show optical isomerism.
Note : Square planar complexes do not show optical isomerism.

ORGANOMETALLIC COMPOUNDS
Compounds containing at least one metal carbon bond may be called organometallic compounds.

Classification of Organometallic Compounds

1. -bonded complex : In a -complex, a metal and a carbon atom of ligand are joined together with
a sigma bond. Examples
R2Cd RMgX R2Zn and
Dialkyl cadmium Alkyl magnesium halide Dialkyl zinc

(CH3 )4 Sn and (CH3 )3 Al are -bonded organometallic compounds.

Tetramethyltin Trimethyl alu min ium

H3C CH3 CH3

Al Al
H3C CH3
CH3
Trimethyl aluminium

2.  –bonded complex : These are organometallic compounds which involve the use of  –bonds
present in organic compounds.

–
2

Cl CH
2
CH Fe Cr
Pt +
K
Cl Cl

Zeisse's salt Ferrocene Dibenzene chromium

2 5 6
K[Pt.Cl3( –C2H4)] Fe( – C5H5)2 Cr( – C6H6)2
3.  and  bonded organometallic compound.
e.g., Ni(CO)4
Fe(CO)5

42 XII - Chemistry
Co - ordination Compounds

Application of Coordination Compound

Applications of co-ordination compounds in analytical chemistry
Gravimetric estimation of metals. The transition metal ions may be estimated by adding a ligand
solution to the metal ion solution under suitable conditions to form an insoluble precipitate of metal ligand
complex of definite stoichiometric composition.

OH O

1. CH3  C  NOH CH3 C N N C CH3

NH OH
|  Ni2   4 Ni
CH3  C  NOH CH3 C N N C CH3
Dimethyl glyoxime

O OH

Nickel dimethylglyoxime complex (red ppt)

2. Volumetric estimation of metals: Complexometric titrations buffer to maintain the desired pH.
EDTA is taken in the burette and added dropwise till the indicator changes its colour at the end
point.
3. To remove the hardness of water via EDTA complex formation.
ORGANOMETALLIC COMPOUNDS
Organometallic compounds are defined as "compounds containing one or more metal-carbon bonds".
The compounds of metalloids such as germanium and antimony and of non-metal like boron, silicon
and phosphorus are also categorized in this title. For example, dialkyl zinc (Frankland reagent), dialkyl
cadmium, alkyl magnesium halides (Grignard's reagents) etc. are the organometallic compounds as they
contain metal-carbon linkage.
Metal carbonyls are also organometallic compounds.
Classification of organometallic compounds:
They can be broadly classified into two categories:
(a)  -bonded compounds:
In these compounds the metal atom is linked to carbon atom by a  -bond. These are formed mostly
by metalloids. Some examples of  -bonded organo metallic compounds are:
(i) Grignard's reagents:
They are represented by the general formula R – Mg – X where R is an alkyl or aryl
group and X is a halogen. These are important organic synthetic reagents. They were
discovered by Victor Grignard in 1900 and hence their name. An example of Grignard's
reagent is C2H5 – Mg – Br (ethyl magnesium bromide).
(ii) Alkyl metals:
Metals such as Zn, Cd, Sn, Pb and mercury form the following organo-metallic compounds:

 CH 3 2 Zn known as Frankland's reagent. It is Dimethyl zinc highly inflammable in

contact with air.

XII - Chemistry 43
 Co - ordination Compounds

 CH3 2 Cd  C2 H5 4 Pb
Dimethylcadmium Tetra ethyl lead

 used as an antiknock 
 compound 
 

(iii) Trialkyl aluminium (R3Al):

Trimethyl aluminium exists as a dimer. In combination with Ti Cl4, it is used as a catalyst
under the name Zeigler Natta catalyst.
(b)  -bonded compounds:
The type of organo-metallic compounds are generally given by transitional elements. The metal-
carbon bonding is not simple covalent but the two are held together by  -electrons.
Examples are:
(i) Organometallics by olefins:
Ethylene and chloroplantinate yield the  -bonded compound known as Zeise's salt.

K PtCl3  2  C2 H4 
Zeise 's salt

(ii) Sandwitch compounds:

Cyclopentadiene, benzene, etc. give  -bonded sandwitch type of compounds with
transition metals.
Examples are ferrocene, dibenzene chromium, etc.

 Fe  5  C5 H5   : Ferrocene, it has aromatic character..

 2

 Cr  6  C 6 H 6   : Di-benzene chromium.
 2

The greek letter (eta) followed by a number indicates the number of carbon atoms
5
  bonded to the metal atom. Thus  in ferrocene shows that the five carbon atoms
in cyclopentadiene are bonded to iron atom.
(c)  -and  -bonded compounds:
Metal carbonyls are the co-ordination complexes of transitional metals in their zero oxidation state
with carbon monoxide. The carbon monoxide acts as a ligand. The metal-carbon bond in metal
carbonyls possess both  and  -bond character. Transitional metals of groups 6, 7, 8, 9 and 10
give carbonyls which are volatile and possess diamagnetic character. Some typical metal carbonyls
are
CO
CO CO
OC  M  CO CO CO
OC  Fe Ni
OC CO CO CO CO
CO CO
M  CO 6
Fe  CO 5 Ni  CO 4
where M  Cr, Mo
(Trigonal bipyramidal) (Tetrahedral)
or W  tungston 

44 XII - Chemistry
Co - ordination Compounds

Synthesis of organometallic compounds:

There are the following important methods of forming metal–carbon bonds.
(a) Preparation of Grignard's reagents:
These are obtained by treating alkyl halides with Mg in the presence of dry ether.

R  X  Mg  dry
ether
  R  Mg  X
Alkyl halide Grignard ' s reagent

Example:

dry ether
C 2 H 5 Br  Mg   C 2 H 5 MgBr
Ethyl bromide Ethyl magnesium bromide

Aryl halides give Grignard's reagent with magnesium in the presence of tetrahydrofuran as
solvent.

tetrahydrofuran
C6 H5  Br  Mg   C6 H5  Mg  Br
Bromo benzene Phenyl magnesium bromide
(Grignard ' s reagent)

(b) Preparation of organo alkali compounds:

These are obtained by the reaction between an alkali metal and alkyl halide in the presence
of ether as solvent.

R  X  2M 
 R  M  MX
Organoalkali

where M = Li, Na or K X = Cl, Br or I.

For example,

 CH3  CH2   CH2  Li  LiCl

CH3  CH 2  CH 2  CH 2  Cl  2Li 
2
n  Butyl chloride n  Butyl lithium

(c) Preparation of tetra alkyl tin:

By the reaction of alkyl lithium with stannic chloride.

SnCl 4  4 Pr Li 
 Pr4 Sn  4LiCl
Tetra propyl tin

(d) Preparation of tetra alkyl lead:

These are obtained when lead tetrachloride is treated with Grignard's reagent. For example,

  C2 H5 4 Pb  4MgBrCl
PbCl4  4C2 H5 MgBr 
Tetra ethyl lead

XII - Chemistry 45
 Co - ordination Compounds

(e) Preparation of metal carbonyls:

These compounds are generally prepared by the direct reaction of the metal and carbon
monoxide under suitable conditions.
2550ºC 
Ni  4CO  Ni  CO  4
Nickel Nickel tetra carbonyl
 Fe  CO 5
Fe  5CO 
Iron pentacarbonyl

(f) Preparation of  -complexes:

 -bonded complexes such as di-benzene chromium, forrocene, Zeise's salt, etc. are prepared
by specific methods illustrated as follows:
   C 6 H 6 2 C r 
2C6H 6  Cr  
B e n ze ne D ib e n zen e ch ro m iu m

  C5 H 5 2 Fe   2MgBrCl
2C5 H 5 MgBr  FeCl2 
Cyclopenta dienyl
magnesium bromide
(Grignard ' s reagent)
2 
CH 2  CH 2   PtCl4     C 2 H 4  PtCl3   Cl 

Ethylene Tetra chloro  Zeise ' s salt
platinate(II)

Application of organometallics:
(a) As homogeneous catalyst:

Wilkinson's catalyst   C6 H 5 3 P  3 RhCl is employed as a homogeneous catalyst for hydrogenation

of olefins (alkenes).
(b) As heterogeneous catalysts:
Zeigler Natta catalyst, a co-ordination complex of trialkyl aluminium and titanium tetrachloride is
used for polymerisation of alkenes.
(c) Organic synthesis:
Organometallics like Grignard's reagent, Dialkyl cadmium, alkyl lithium, etc., are used as synthetic
tools for the preparation of almost all types of organic compounds.
(d) As petrol additive:
Tetraethyllead (TEL) is used as an important antiknock compound in petrol.
(e) For refining of metals:
The easy formation and thermal decomposition of metal carbonyls is used in the extraction and
purification of metals. For example, Ni is refined by Mond's process which involves the formation
and decomposition of nickel tetracarbonyl.
(f) In medicine:
Syphilis is cured by using organo arsenic compounds.
(g) In agriculture:
Seeds are treated with ethyl mercury chloride to protect the plants against infection.

46 XII - Chemistry
Co - ordination Compounds

CBSE SECTION
VERY - SHORT - ANSWER QUESTION
1. What is the difference between double salt and a complex compound?

2. Define a 'ligand'. Give an example.

3. Which of these cannot act as ligand : NH3, H2O, CO, CH4?

4. How is ammonia molecule a good ligand?

5. What is bidentate ligand? Give one example.

6. Define coordination number.

7. What are the most common coordination nos. encountered in coordination compounds?

8. How many coordination sites are there in ethylene diamine?

9. What is coordination polyhedron?

10. What is the coordination no. of a central ion in octahedral complex? Why does NH3 from complex but
NH4+ ion does not?

11. What is the coordination number of central metal ion in [Fe(C2O4)3]–?

12. Give one example of chelate complex.

13. What is the charge on the complex of Pt2+ in which the ligands are – one water molecule, one pyridine
molecule and one ethylene-diamine molecule?

14. Write the structures of a pair of complexes showing geometrical isomerism.

15. How many isomers are there for the complex [Co(NH3)4Cl]Cl?

16. Name the type of isomerism that occurs in complexes in which both cation and anoin are complex ions.

17. How many isomers are there for octahedral complex [CoCl2(en)(NH3)2]+?

18. Illustrate the geometrical isomers of [Pt(NH3)4Cl2]2+.

19. Why does a tetrahedral complex of the type [MA2B2] not show geometrical isomerism?

20. In the geometry of a complex compound the molecule is trigonal bi-pyramidal. What is the hybridization
of the central atom?

21. If the geometry of [PtCl4]2– is square planar, which orbitals of Pt are involved in the bonding?

22. What is oxidation state of Co in complex [Co(NH3)2(NO2)Cl] [Au(CN2]?

23. How many moles of AgCl will be precipitated when an excess of AgNO3 is added to a molar solution of
[CrCi(H2O)5 ]Cl2 ?

XII - Chemistry 47
 Co - ordination Compounds

24. What scheme of hybridization is proposed for Co in [Co(NH3)6]3+?

25. Write an anion whose shape can be explained by the scheme of sp3d2 hybridization.

SHORT - ANSWER - QUESTIONS

1. Differentiate between a double salt and a complex with the help of an example.

2. Illustrate the following with examples:

(i) Ambident ligand

(ii) chelating ligand.

3. Define primary coordination sphere. Illustrte it with an example.

4. What is meant by hexadentate ligand? Give one example. How is such a ligand useful for measuring
hardness of water?

5. What are homoleptic and heteroleptic complexes. Give an example of each type.

6. Square planer complexes with a coordination number 4 exhibit geometrical isomerism whereas tetrahe-
dral complexes do not, why?

7. Write all isomers of [Co(NH3)5NO2]Cl2.

8. Illustrate the geometrical isomerism in corrdination compounds with one example.

9. What is solvate isomerism? Give an example.

10. A coordination compound has the formula CoCl3.4NH3. It does not liberate ammonia but precipitates
chloride ion as AgCl. Give the IUPAC name of the complex and write its structural formula.

11. Illustrate with an example the ionization isomerism in coordination compounds.

12. Explain geometrical isomerism with reference to square planar complexes giving one example. Why is
it so that tetrachedral complexes with simple ligands do not exhibit geometrical isomerism?

13. Differentiate between inner and outer orbital complex. Give an example of each tyep.

14. Using valence bond theory of complexes, explain the geometry and diamagnetic nature of the ion
[Co(NH4)6]3+ [At. No. of Co = 27]

15. Using valence bond theory, explain the bonding in [Cr(H2O)6]3+ [At. No. of Cr = 24].

16. Using valence bond theory, predict the geometry and magnetic character of [NiCl4]2–. Atomic no. of Ni
is 28.

17. Describe the shape of tetracyanidonicklate (II) ion and account for its magnetic property.

18. Using valence bond theory, predict the shape and magnetism (paramagnetism) or diamagnetism of
[Co(CO)4]–, (At. No. of Co = 27).

48 XII - Chemistry
Co - ordination Compounds

19. In a complex ion : [Co(NH3)3(H2O)2Cl]+

(a) Identify the ligand's formula and the charge on each one of them and

(b) Write the geometry of complex ion.

20. Explain how [Pt(NH3)2Cl2] and [Pt(NH3)6Cl2 will differ in their electrolytic conductances. Give the
hybridization state of Pt in these compounds. (At. No. of Pt is 78).

LONG - ANSWER - QUESTIONS

1. How would you account for the following:

(a) [Ti(H2O)6]3+ is coloured while [Sc(H2O)6]3+ is colourless,

(b) [Fe(CN)6]3+ weakly paramagnetic while [Fe(CN)6]4– is diamagnetic,

(c) Ni(CO4) possess tetrahedral geometry, while [Pt(NH3)2Cl2] is square planar and diamagnetic?

2. (a) Write the formula of the following complexes:

(i) Hexaammineplatinum (IV) chloride

(ii) Dichloridotetraamminecobalt (III) ion

(b) Using valence bond theory of complexes, explain the geometry and magnetic nature of [Co(NH3)6]3+
(At. no. of Co = 27)

OR

(a) The value of dissociation constant of [Cu(NH3)4]2+ and [Co(NH3)6]3+ are 1.0 × 10–12 and 6.2 ×
10–36 respectively. Which complex would be more stable and why ?

(b) Using valence bond theory of complexes, explain the geometry and magnetic nature of [Ni(NH3)6]2+
(At. no. of Ni = 28)

3. (a) A coordination compound has the formula CoCl3 4NH3. It does not liberate NH3 but forms a
precipitate of AgCl on treatment with AgNO3 solution. Write the structure and IUPAC name of
the complex.

(b) Write two properties of the central metal ion which enable it to form stable co9mplex entitites.

(c) The formation of complex compounds finds application in the extraction of some metals. Furnish
one example to support the above statement.

4. Draw a sketch to show the splitting of d-orbitals in an octahedral crystal field. State clearly how the
actual configuration in split d-orbitals in an octahedral crystal field is decided by the magnitutdes of  0
and P.

5. Describe for any two of the following complex ions, the type of hybridization, shape and magnetic
property:

(i) [Fe(H2 O) 6] 2+ (ii) [Co(NH3 )6 ]3+ (iii) [NiCl4]2–

(At. Nos. Fe = 26, Co = 27, Ni = 28)

XII - Chemistry 49
 Co - ordination Compounds

6. (a) Give the IUPAC name of [CrCl2(H2O)4]Cl

(b) Give the number of unpaired electrons in the following complex ions:

[FeF6]4– and [Fe(CN)6]4–

(c) Name the isomerism exhibited by the following pair of coordination compounds:

[Co(NH3)5Br]SO4 and [Co(NH3)5 SO4 ]Br

Give one chemical test to distinguish between these two compounds.

7. Give the electronic configuration of the
(a) d-orbitals of Ti in [Ti(H2O)65]3+ ion in an octahedral crystal field.
(b) Why is this complex coloured? Explain on the basis of distribution of electrons in the d-orbitals.
(c) How does the colour change on heating [Ti(H2O)6]3+ ion?

50 XII - Chemistry