CHAPTER: 9 COORDINATION COMPOUNDS

INTRODUCTION:
Coordination compounds are the inorganic salts formed by the combination of two or
more simple salts in stoichiometric ratios.
They are stable in solid state as well as in solution. They are widely present in plants, animals and
minerals.
 Chlorophyll is a magnesium complex present in plants.
 Haemoglobin is an iron complex present in animals (blood).
 Cryolite is an aluminum complex present in minerals.

TYPES OF INORGANIC SALTS:

1. SIMPLE SALTS:
The compounds made up of one acid radical and one basic radical are called simple salts.
Examples: CaCl2, KNO3, NaCl, etc.

2. DOUBLE SALTS:
The compounds made up of two simple salts are called double salts.
Examples: Mohr’s salt: FeSO4. (NH4)2.SO4. 6H2O
Potash alum: K2SO4. Al2(SO4)3. 24H2O
Carnallite: KCl. MgCl2. 6H2O

Note: Both simple and double salts are stable only in solid state because they dissociate into their ions
when dissolved in water. Hence their solution gives the reactions of all the ions present in them.

3. COORDINATION COMPOUNDS:
The compounds containing at least one complex ion in which the central metal atom or ion is
surrounded by certain number of molecules or ions through coordinate bond are called co-
ordination compounds.
These compounds are stable and retain their properties in solid state as well as in solution.
Examples: K4[Fe(CN)6] - Potassium ferrocyanide
[Ni(CO)4] - Nickel tetracarbonyl
[Cu(NH3)4]SO4- Cupprammonium sulphate

DIFFERENCE BETWEEN DOUBLE SALTS AND COMPLEX COMPOUNDS:

DOUBLE SALTS COMPLEX COMPOUNDS

They are made up of two simple salts. They contain at least one complex ion.

Complex compounds are formed through

They are ionic in nature.
coordinate bond. They may or may not be ionic.

They are stable only in their solid state where as

They are stable in their solid state as well as in
in aqueous solutions they dissociate into their
aqueous solutions.
constituent ions.
They dissociate into complex ions and simple
They dissociate into simple ions in solution
ions.
TERMS USED IN CO-ORDINATION COMPOUNDS:

1. COORDINATION ENTITY OR COMPLEX ION:

Coordination entity or complex ion constitutes a central metal atom or ion bonded to certain
number of ions or molecules called ligands.

Example: [Co(NH3)3Cl3] is a co-ordination entity, in which cobalt (+3) ion is the central metal atom
which is surrounded by three NH3 molecules and three negatively charged chloride ions.
Other examples are [Ni(CO)4], [Fe(CN)6]4-, [PtCl4]2-,etc..

TYPES OF COMPLEX IONS:

a. CATIONIC COMPLEX:
A coordination compound which has positively charged complex ion.
Examples: [Co(NH3)6]3+, [Ni(NH3)6]2+ etc..

b. ANIONIC COMPLEX:
A coordination compound which has negatively charged complex ion.
Examples: [Fe(CN)6]4-, [Ag(CN)2]1- etc..

c. NEUTRAL COMPLEX:
A coordination compound which has no charge on complex entity.
Examples: [Ni(CO)4], [Co(NH3)3Cl3] etc..

Note: A neutral complex doesn’t have an ionisation sphere.

2. CENTRAL METAL ATOM OR ION:

The metal atom or ion which is bonded to fixed number of ions or molecules in a co-ordination
entity is called central metal atom or ion.
Examples: The central metal atom or ions in [Cu(NH3)4]2+,[Fe(CN)6]4-, [Ni(H2O)4Cl2] and [Ni(CO)4] are
Cu2+, Fe2+, Ni2+ and Ni respectively.

3. LIGANDS:
Ligand is an ion/ molecule which is capable of donating at least a lone pair of electrons to the
central metal atom/ion and forms coordinate covalent bond.
OR
An ion/ molecule bonded to the central metal atom / ion through a co-ordinate bond in the
coordination entity is called as ligand.

LIGATING ATOM:
The atom in the ligand which can donate electron pair is called donor atom/ coordinating atom /
ligating atom.

Note: In all the coordination compounds, central metal atoms are Lewis acids and ligands are
Lewis bases.

CLASSIFICATION OF LIGANDS:
Based on the number of donor atoms available for coordination with the central metal atom,
ligands are of the following types.
1. MONODENTATE OR UNIDENTATE LIGANDS: Ligands which coordinate with the central metal
atom or ion through only one donor atom are called as Monodentate or Unidentate ligands.
Examples for negatively charged monodentate ligands: (name ending with ‘O’)
Symbol Name as ligand Symbol Name as ligand
- fluorido SCN- thiocyanato
F
Cl- chlorido NCS- Isothiocyanato

Br- bromido NO3- nitrato

I- Iodido OH- hydroxido

NO2- nitrito-N CN- cyanido
ONO- nitrito-O NH2- amido

Examples for neutral monodentate ligands:

Symbol Name as ligand Symbol Name as ligand

NH3 ammine C5H5N pyridine(py)
CO carbonyl P(C6H5)3 triphenylphosphine
NO nitrosyl CH3NH2 methylamine
H2O aqua PH3 phosphine

Examples for positively charged monodentate ligands: (name ending with ‘ium’)
+ + +
NO 2 NO NH 2-NH 3
nitronium nitrosonium hydrazinium

2. BI-DENTATE LIGANDS:
Ligands which coordinate with the central metal atom or ion through two donor atoms are called as
bidentate ligands.
Examples:
- .. ..
COO CH2NH2 CH3- C=N-OH
- .. .. .. -
COO CH2NH2 CH3- C=N-OH H2N-CH2-COO
oxalate ion(ox) Ethane-1,2-diamine(en) dimethyl glyoxime(dmg)
  glycinate ion
Note: The bidentate ligands in which two coordinating atoms are same are called symmetrical bi-
dentate ligands.
Example: oxalate ion, ethane-1, 2-diamine, dimethyl glyoxime.

The bidentate ligands in which two coordinating atoms are different are called unsymmetrical bi-
dentate ligands.
Example: glycinate ion.

3. POLY DENTATE LIGANDS: Ligands having more than two donor are called poly dentate ligands.

I. TRI DENTATE LIGANDS: Ligands which can coordinate to the central atom through three donor
atoms.
Example:

.. .. ..
H2N-CH2-CH2-NH-CH2-CH2-NH2
      diethylene triamine  
II. TETRA DENTATE LIGANDS: Ligands which can coordinate to the central atom through four donor
atoms.
Examples:
.. .. .. ..
H2N-CH2-CH2-NH-CH2-CH2-NH-CH2-CH2-NH2
triethylene tetraamine  

III. PENTA DENTATE LIGANDS: Ligands which can coordinate to the central atom through five donor
atoms.
Example s:
_
_ .. .. CH2-COO
OOC-H2C -HN-CH2-CH2-N _
CH2-COO
3-
ethylenediaminetriacetate ion (edta)  
 
IV. HEXA DENTATE LIGANDS: Ligands which can coordinate to the central atom through six donor
atoms.
Examples:
_ _
OOC-H 2C .. .. CH 2-COO
_ N-CH 2-CH 2-N _
OOC-H 2C CH 2-COO
4-
ethylenediaminetetraacetate ion (edta)  

AMBIDENTATE LIGANDS:
The mono dentate ligands containing more than one donor atom but coordinate with central
metal atom using one of the donor atoms at a time.
Example: NO2 can coordinate to the metal atom through nitrogen or oxygen.

M O-NO M NO2
Nitrito-O (Nitrito) Nitrito-N (Nitro)

M CN M NC
Cyanido Isocyanido

M SCN M NCS
Thiocyanato Isothiocyanato  

CHELATING LIGAND AND CHELATE:

A di or a poly dentate ligand which uses its two or more donor atoms to bind to the same central
metal and form ring structure in a co-ordination compound is called a chelating ligand. The resulting
complex is called chelate.

Example:
.. .. .. 2+
CH2-H2N CH2-H2N NH2-CH2
.. .. Cu ..
CH2-H2N CH2-H2N NH2-CH2
Chelating ligand Chelate complex  
 
DENTICITY:
The number of ligating atoms present in a ligand indicates the denticity of the ligand.
Example: Denticity of ethane-1,2-diamine(en) ligand is two.
Denticity of oxalato (ox) ligand is two
Denticity of ethylene diamine tetraacetate (edta)4- is six.

COORDINATION NUMBER:
The total number of coordination bonds formed by the central metal atom or ion with the
ligands is called coordination number.
Example: Coordination number of Ni in [Ni(CO)4] is four because nickel atom is surrounded by four
carbonyl ligands forming four coordinate bonds.
[Ag(CN)2]- Coordination number of Ag+ ion is 2
[Ni(NH3)4]2+ Coordination number of Ni2+ ion is 4
[Pt Cl6]-2 Coordination number of Pt4+ ion is 6

COORDINATION SPHERE:
The part of the coordination compound containing the central metal atom and ligands directly
attached to the central metal atom is called coordination sphere of the coordination compound.
The coordination sphere is written in square bracket. This part of the coordination compound does not
ionize. The ionisable groups written outside the bracket are called counter ion.
Ligands
Coordination entity / complex ion

Coordination sphere Ni (NH 3) Cl 2 Ionisation sphere

6 (Counter ion)

Central metal ion

Coordination number

OXIDATION NUMBER OF CENTRAL METAL ATOM:

The oxidation number of a central metal atom/ ion in a complex is defined as the charge carried
by central metal atom if all the ligands are removed with the electron pair that are shared with
the central metal atom/ion.

Example: [Ni(NH3)6]2+ : x + 6(0) = +2 x = +2 O.N of Ni is +2

K4[Fe(CN)6] : 4(+1) + x + 6(-1) =0 x = +2 O.N of Fe is +2
Note: The oxidation number of central metal atom is represented in roman numerical in IUPAC
system of naming of co-ordination compounds.

HOMOLEPTIC AND HETEROLEPTIC COMPLEX:

Homoleptic complexes are the co-ordination compounds in which the central metal atom or ion
is surrounded by only one type of ligand.
-
Example: [Cu(NH3)4] 2+, [Ni(CO)4], [Fe(CN)6]3-, [Ag(CN)2]

Heteroleptic complexes are the co-ordination compounds in which the central metal atom or ion
is surrounded by two or more different types of ligands.
Example: [Pt(NH3)2Cl2], [Co(NH3)4Cl(NO2)]1+
COORDINATION POLYHEDRON:
The spatial arrangement of ligands attached to the central metal atom or ion in the coordination
sphere is called co-ordination polyhedron.
This gives the geometry of complex depending on the number of ligands.
L L L L

L L L L L
M L L
L M M L M M
L L L L L L L L L

L
L
Tetrahedral Square planar Square pyramidal Trigonal Octahedral
bipyramidal

NOMENCLATURE OF CO-ORDINATION COMPOUNDS:

The formulae and names adopted for coordination entities are based on the recommendations of the
International Union of Pure and Applied Chemistry (IUPAC).

NAMING OF MONO-NUCLEAR CO-ORDINATION COMPOUNDS:

1. In coordination compounds, cations are named first followed by the name of the anion.
Example: [Cu(NH3)4]SO4, [Cu(NH3)4]2+ is a cation named first followed by anion SO42-.

2. NAMING THE COMPLEX ION: Ligand metal (O.S of central metal in roman numerical)
a) If two or more different types of ligands are present, they are named in the alphabetical order.
Example: chloride and ammine groups are named as amminechlorido.
ammine and aqua ligands are named as ammineaqua.

b) Two or more identical ligands are named using the prefix di, tri, tetra, penta etc…

c) If the name of the ligand itself contains a numerical prefix, the ligands are named using prefixes like
bis for 2, tris for 3, tetrakis for 4, pentakis for 5, etc.. and written with in parenthesis.

3. Naming the central metal:

a) If the complex entity is a positive ion or neutral, the central metal ion is named as such.
b) If the complex entity is a negative ion, the name of the central metal ion ends with ‘ate’ preferably
using their Latin names.

Latin names of certain metals:

Tin (Sn) Lead (Pb) Gold (Au) Silver (Ag) Iron (Fe) Copper (Cu)
Stanate Plumbate Aurate Argentate Ferrate Cuprate

4. Oxidation number of a central metal atom or ion is indicated by roman numerical in the parenthesis.
Examples: Co3+ ion is represented as cobalt (III)
Cu2+ ion is represented as copper (II)
NOMENCLATURE OF SOME TYPICAL COMPLEX IONS, AND COORDINATION COMPOUNDS:

Sl. No. FORMULA IUPAC NAME

1 [Ag(NH3)2]Cl diamminesilver(I) chloride

2 [Cu(NH3)4]SO4
3 [Cr(H2O) 4Cl2]NO3
4 [Cr(H2O)6]Cl3
5 [Pt (NH3)2Cl2]
6 [Pt(NH3)3Cl2(NO2)]2SO4
7 [Pt (NH3)4Cl2]Br2
8 [Co(NH3)6]Cl3
9 [Co(NH3)3(NO2)3]
10 [Ni(dmg)2]
tetramminecopper(II) sulphate
tetraaquadichloridochromium(III) nitrate
hexaaquachromium(III) chloride
diamminedichloridoplatinum(II)
triamminedichloridonitrito-N-platinum(V) sulphate
tetraamminedichloridoplatinum(IV) bromide
hexaamminecobalt(III) chloride
triamminetrinitrito-N-cobalt(III)
bis(dimethylglyoximato)nickel(II)

11 [CoCl(en)2(NO2)]+ chloridobis(ethylenediammine)nitrito-N-cobalt(III) ion

12 Na[Au(CN)2] sodium dicyanidoaurate(I)
13 K2[PtF6] potassium hexafluoridoplatinate(IV)
14 K[Ag(CN)2] potassium dicyanidoargentate(I)
15 K[Pt (NH3) Cl5] potassium amminepentachloridoplatinate(IV)
16 K3[Fe(CN)6] potassium hexacyanidoferrate(III)
17 K4[Fe(CN)6] potassium hexacyanidoferrate(II)
18 NH4[Cr(NH3)2(SCN)4] ammonium diamminetetrathiocyanatochromate(III)
19 K3[Fe(C2O4)3] potassium trioxalatoferrate(III)
20 Na2[Ni(edta)] sodium ethylenediaminetetraacetatonickelate(II)
21 [Cu(NH3)4(H2O)2]SO4 tetraamminediaquacopper(II) sulphate

22 [Ni(CO)4] tetracarbonylnickel(0)
23 [Pt(NH3)4][PtCl4] tetraammineplatinum(II) tetrachloridoplatinate(II)

24 [Co (NH3)4Cl2]3[Cr(CN)6] tetraamminedichloridocobalt(III) hexacyanidochromate(III)

RULES FOR WRITING THE FORMULA OF MONONUCLEAR COORDINATION ENTITY:

A mononuclear coordination entity contains a single central metal atom. The following rules are applied
while writing the formulae
1. The central metal atom is listed first in the left.
2. The symbol or formula of ligands is then represented towards right side of the metal in the
alphabetical order of their names.
Example: 4-chlorido and 2-ammine ligands ligated to platinum are written as [Pt(NH3)2Cl4]
3. The metal atom and ligands are written inside the square brackets to indicate the complex entity.
4. Polyatomic molecules or ions of ligands are represented in the parenthesis.
Example: 6 CN- ligands are represented as (CN)6.
5. Certain ligands are represented in abbreviations in parenthesis.
Example: 2-dimethyl glyoximato are represented as (dmg)2
6. The alphabetical order should be considered only for the names of the ligand and not for the
prefixes used for ligands.
7. The algebraic sum of the oxidation number of all atoms in the co-ordination entity is written outside
the square bracket as a superscript. (the number should be written first followed by the sign)
8. The charge of cation is always balanced by the charge of the anion.
Example: [Cu(NH3)4]2+ SO4-2, +2 charge of complex ion is balanced by -2 charge on sulphate ion.

IUPAC name of the co-ordination compound Formula of the co-ordination compound

tetrahydroxozincate(II) ion [Zn(OH)4]2-

pentaaquachloridochromium(III) chloride [Cr(H2O)5Cl]Cl2

tetraamminedichloridocobalt(III) ion [Co(NH3)4Cl2]+

tetraaquazinc(II)ion [Zn(H2O)4]2+

pentacarbonyliron(0) [Fe(CO)5]

diamminedichloridoplatinum(IV) ion [Pt(NH3)2Cl2]2+

dicyanidoargentate(I) ion [Ag(CN)2]-

hexaamminecobalt(III) chloride [Co(NH3)6]Cl3

potassium tetracyanidonickelate(II) K2[Ni(CN)4]

triamminetrichloridocobalt(III) [Co(NH3)3Cl3]

tetraamminechloridonitrito-N-cobalt(III)ion [Co(NH3)4Cl(NO2)]+

potassium hexathiocyanatocobaltate(III) K3[Co(SCN)6]

chloridobis(ethylenediammine)nitrito-N-cobalt(III) [CoCl(en)2(NO2)]+
ion
diamminesilver(I) chloride [Ag(NH3)2]+
tetramminecopper(II) sulphate [Cu(NH3)4]SO4

ISOMERISM IN COORDINATION COMPOUNDS:

Two or more compounds which have same molecular formula but different structural or spatial
arrangement of atoms are called isomers and the phenomenon is called isomerism.
(Greek: Iso means equal, meros means parts)
Isomerism exhibited by co-ordination compounds can be classified into two types:
1. Structural isomerism
2. Stereo isomerism or space isomerism.

1. STRUCTURAL ISOMERISM:
Two or more co-ordination compounds having same molecular formula but differ in the
structural arrangement of ligands around the central metal atom are called structural isomers
and the phenomenon is called structural isomerism.
Structural isomerism exhibited by coordination compounds is further classified into four types:
a) IONISATION ISOMERISM:
Two or more co-ordination compounds having same molecular formula but gives different ions
on dissolution in a solvent are called ionization isomers and the phenomenon is called
ionisation isomerism.
In this type of isomerism, there is exchange of groups between the co-ordination sphere of metal ion
and the counter ion.
Example:
2+ 2-
[Co(NH 3)5Br]SO 4 [Co(NH 3)5Br] + SO 4
pentamminebromidocobalt(III) sulphate gives w hite ppt w ith
(red violet) Barium chloride

+ –
[Co(NH 3)5(SO 4)]Br [Co(NH 3)5(SO 4)] + Br
pentamminesulphatocobalt(III) bromide gives pale yellow ppt w ith
(red) silver nitrate

Other compounds showing this type of isomerism are:

[Co(NH3)5(NO2)]SO4 and [Co(NH3)5(SO4)]NO2
[Pt(NH3)4Cl2]Br2 and [Pt(NH3)4Br2]Cl2
[Co(NH3)5(NO3)]SO4 and [Co(NH3)5(SO4)]NO3

b) LINKAGE ISOMERISM:
Two or more co-ordination compounds having same molecular formula but differs in the mode
of attachment of ligands (ambidentate) to the central metal atom or ion are called linkage
isomers and the phenomenon is called linkage isomerism.
This type of isomerism arises when the coordination sphere contains Ambidentate ligands.
Examples:
2+ NH3 2+
NH3

H 3N NO 2 H 3N ONO

Co Co

H 3N NH3 H 3N NH3

NH3 NH3

pentaamminenitrito-N-cobalt(III) ion pentaamminenitrito-O-cobalt(III) ion

    (yellow)   (red)

-
In the given examples the Ambidentate ligand is NO2 . It can coordinate with a central metal ion
through oxygen or nitrogen atom. If the bonding is through N, the ligand is named as nitrito-N and if it is
through O, it is named as nitrito-O.

Other compounds showing this type of isomerism are:

[Cr(H2O)5(SCN)]2+ and [Cr(H2O)5(NCS)]2+ , [Mn(CO)5(SCN)] and [Mn(CO)5(NCS)]

c) HYDRATE / SOLVATE ISOMERISM:

Two or more co-ordination compounds having same molecular formula but differs in the
number of water molecules present as ligands or as molecules of hydration (water of
crystallisation) are called hydrate isomers and the phenomenon is called hydrate isomerism.
Examples: The three isomers having the molecular formula CrCl3 .6H2O.

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

Violet Blue green Green
[Cr(H2O)6]Cl3 complex has three ionisable chloride ions and with AgNO3 gives three moles of AgCl per
mole of the complex. The [Cr(H2O)5Cl]Cl2.H2O and [Cr(H2O)4Cl2]Cl.2H2O complex has two and one
ionisable chloride ions respectively and with AgNO3 gives two moles of AgCl and one mole of AgCl per
mole of the complex respectively.
Other compounds showing this type of isomerism are:
[Co(NH3)4(H2O)Cl]Br2 and [Co(NH3)4BrCl]Br.H2O
[Co(H2O)Cl(en)2]Cl2 and [CoCl2(en)2]Cl.H2O

d) COORDINATION ISOMERISM:
Two or more co-ordination compounds having same molecular formula, containing both
complex cation and complex anion but differs in the distribution of ligands in the coordination
entity of cationic and anionic parts are called co-ordination isomers and the phenomenon is
called co-ordination isomerism.
This type of isomerism arises from the interchange of ligands by the cationic and anionic entities of
different metal ions present in the complex.
Examples: [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
[Cu(NH3)4] [PtCl4] and [Pt(NH3)4] [CuCl4]
[Co(en)3] [Cr(CN)6] and [Cr(en)3] [Co(CN)6]

2. STEREO ISOMERISM:
Co-ordination compounds having same molecular formula and structural formula but differ in
the spatial arrangement of ligands around the central metal atom or ion in a coordination
compound is called stereo isomers and the phenomenon is called stereo isomerism.
There are two types of stereo isomerism namely:
a) Geometrical isomerism
b) Optical isomerism

a) GEOMETRICAL / CIS-TRANS ISOMERISM:

Geometrical isomerism arises in heterolyptic complexes due to the ligands occupying different
geometrical position around the central metal atom.
There two ways of arranging the ligands:
 When similar ligands occupy the adjacent positions, the arrangement is represented as cis
isomerism.
 When similar ligands occupy the opposite positions, the arrangement is represented as trans
isomerism.

GEOMETRICAL ISOMERISM IN COMPLEXES OF CO-ORDINATION NUMBER FOUR (4):

The complexes having co-ordination number 4 has two geometry, which is tetrahedral and square
planar geometry.
Note:
 The geometrical isomerism is not possible in tetrahedral complexes because the ligands attached to
the central metal atom are all adjacent (equivalent) to each other. Only square planar complexes
exhibits geometrical isomerism.
 The complexes of the type Ma2b2, Mabx2, Mabcd and M(ab)2 type exhibits cis-trans
isomerism, where a, b, c, d are Monodentate ligands and (ab) is an unsymmetrical bi dentate
ligand. Eg. gly. 1
..
---------------
. 2
..
.
  ... ...
..
M
..
... ...
4 --------------- 3
 In a square planar complex Positions 1-3 and 1-4 are trans while rest are cis i.e 1-2, 2-3, 3-4
and 1-4.

SQUARE PLANAR COMPLEX OF THE TYPE Ma2b2: (one cis and one trans isomerism)
A complex compound showing this type of isomerism is [PtCl2(NH3)2]. It exists in two different forms
i.e., cis and trans forms. The cis form is pale yellow colour while trans form is dark yellow in
colour.
Examples: [Pt(NH3)2Cl2]
---------------... .---------------...Cl
Cl . NH3 H 3N .
.. ...
... .. ..
.. Pt ... ... Pt ...
.
.. .. ..
.---------------
.
..
Cl ---------------. NH3 Cl NH3
cis-isomer trans-isomer
(pale yellow) (dark yellow)
Note: Cis isomer of [Pt(NH3)2Cl2] is called cis-platin which is an anti-cancer agent.

SQUARE PLANAR COMPLEX OF THE TYPE Mabx2: (one cis and one trans isomer)
Examples: [Pt(NH3)2Cl(NO2)]
Cl .
.---------------...
NH3 Cl ..
.
---------------... NH3
... . ... .
. .. Pt ..
... ...
Pt
... ...
.. . .
.--------------- ..
O 2N ---------------.NH3 H 3N NO 2
cis-isomer trans-isomer

SQUARE PLANAR COMPLEX OF THE TYPE Mabcd: (two cis and one trans isomer)
In these complexes, all the four ligands that are linked with the central metal atom or ion are different.
Such compounds can exist as three geometrical isomers.
Examples: [Pt(NH3)(H2O)(NO2)Py]+
+ + +
---------------... py
H 3N.
..
H 3N. ---------------...H2O
..
H 3N . ---------------...H2O
..
.. .. .. .. .. ..
... Pt ... ... Pt ... ... Pt ...
.
.. .. .
.. .. .. ..
O 2N ---------------.H 2O O 2N ---------------.py py .---------------.NO 2

SQUARE PLANAR COMPLEX OF M(ab)2 Type: (one cis and one trans)
Complexes of the formula M(ab)2 can form geometrical isomers if the bi-dentate ligands are
unsymmetrical
-
Examples: platinum glycinato complex [Pt(gly)2] where gly is H2N-CH2-COO
H2N..---------------..NH2 O..---------------..NH2
H 2C .. .. CH O=C .. .. CH
... Pt ... 2 ... Pt ... 2
O=C ... ...
C=O
H2C ... ...
C=O
. .
O ---------------. O H2N---------------. O
cis-isomer trans-isomer .
Note:
The square planar complexes of type Ma4, Max3, Ma3x do not exhibit geometrical isomerism
because all possible spatial arrangements are identical.
COMPLEX COMPOUND WITH CO-ORDINATION NUMBER SIX (6):
The octahedral complexes of type Ma4b2 or Ma2b4, Ma3b3 and M(aa)2b2 exhibits cis-trans isomerism.
1

.---------------...
5. 2
... ..
... M ...
. ..
..
4 ---------------. 3

  6
In a octahedral complex Positions 1-6, 2-4 and 3-5 are trans while the rest are cis i.e 1-2, 1-3, 1-
4, 1-5, 2-6, 3-6, 4-6, 5-6, 2-3, 3-4, 4-5 and 2-5.

1) Ma4b2 TYPE: octahedral complex, [Co(NH3)4Cl2]+ can exist in cis and trans forms. In this case the
cis form is violet in colour while the trans form is green in colour.
Cl Cl
+ +
H 3N. ---------------... Cl
..
H 3N. ---------------...NH3
..
.. .. .. ..
... Co ... ... Co ...
.. .. .. ..
H 3N .---------------.NH3 H 3N .---------------. NH3

NH3 Cl
cis-isomer trans-isomer

2) Ma3b3 TYPE: This type of co-ordination compound exhibits fac and mer isomeric forms.

FACIAL ISOMER:
If three similar ligands are on the same triangular face of the octahedron then the isomers are
called facial isomers or fac isomer.

MERIDIONAL ISOMERS:
If three similar ligands are at the corners of a square plane of the octahedron i.e at the three
adjacent equatorial positions of an octahedron, then the isomers are called meridional isomers
or mer isomer.
Examples: [Co(NH3)3(NO2)3]
NO 2 NH3

H 3N.
..
---------------... NO 2 O 2N.
..
---------------...NO 2
... .. ... ..
.. Co ... .. Co ...
. . . .
H 3N ..
--------------- NO 2 .. H 3N ..
--------------- .. NO 2

NH3 NH3
fac-isomer mer-isomer
M(aa)2b2 TYPE: These complexes should contain symmetrical bidentate ligands (aa) like ethylene
diammine(en) or Oxalato(ox) ions.
Cl + Cl +

.---------------
. .. Cl .---------------
. ..
... ... ... ...
en .. Co . en .. Co .
. .. . .. en
... ... ... ...
--------------- ---------------
en
Cl
cis-isomer trans-isomer  
 b) OPTICAL ISOMERISM:
Stereo isomers that rotate the plane polarized light equally in opposite direction are called
optical isomers and the phenomenon is called optical isomerism.

CONDITIONS:
 To exhibit optical isomerism the molecule should be chiral (chirality) i.e. The molecule should
not have any plane of symmetry.
 Optically active dextro and laevo isomers are nonsuperimposable mirror images of each other.

DEXTRO ISOMER:
Optically active compound that rotates the plane polarized light towards right side is called a
dextro isomer represented as (d) or (+).

LAEVO ISOMER:
Optically active compound that rotates the plane polarized light towards left side is called a
laevo isomer represented as (l) or (-).

OPTICAL ISOMERISM IN COMPLEXES OF CO-ORDINATION NUMBER SIX (6):

Octahedral complexes of type [M(aa)3], and [M(aa)2b2] type exhibit optical isomerism.
1) M(aa)3 type: Example: [Co(en)3]3+
3+ 3+
en en
--------------- ---------------
en Co Co en

--------------- ---------------
Mirror en
en
dextro isomer laevo isomer  
2) M(aa)2b2 type: Example: [CoCl2(en)2]+
Cl + Cl +

--------------- Cl Cl ---------------

en Co Co en

--------------- ---------------
Mirror en
en
dextro isomer laevo isomer
THEORIES OF BONDING IN CO-ORDINATION COMPOUNDS:
Alfred Werner was the first to describe the bonding features in coordination compounds. Many
approaches have been put forth to explain the nature of bonding in coordination compounds namely
Valence Bond Theory (VBT), Crystal Field Theory (CFT), Ligand Field Theory (LFT) and
Molecular Orbital Theory (MOT).

1. WERNER’S THEORY OF COORDINATION COMPOUNDS:

Alfred Werner in the year 1893 proposed a theory known as Werner’s theory of coordination
compounds to explain the bonding in these compounds.
ASSUMPTIONS OF WERNER’S THEORY:
1. In coordination compounds the central metal atom or ion exhibit two types of valencies namely
Primary valency (ionisable valency) and Secondary valency (non-ionisable valency).
2. Primary valency of a metal is equal to the oxidation number/ charge on the metal and
secondary valency is equal to the coordination number of the complex ion that is the number of
coordinate bonds formed by ligands with central metal ion.
3. Primary valency of a metal ion is satisfied by negative ions and the secondary valency is
satisfied by negative ions or neutral molecules that act as ligands.
4. The secondary valency of a metal is arranged in space to give a definite geometrical shape to
the complex depending on the number of ligands.

MERITS OF WERNER’S THEORY:

1. It explains the formation of complex ions satisfactorily.
2. It gives the difference between primary valency and secondary valency.
3. It explains the geometrical shape of the complex ion.

DE-MERITS (LIMITATIONS) OF WERNER’S THEORY:

1. The theory is not based on electronic theory.
2. It cannot explain how a negative ion can satisfy both primary and secondary valency.

2. VALENCE BOND THEORY:

This theory was developed by Linus Pauling to explain magnetic behavior and shapes possessed
by the complex ions.

ASSUMPTIONS OF VALENCE BOND THEORY:

1. The central metal atom or ion present in a complex provides a definite number of vacant orbitals for
the formation of coordinate bond with ligands.
2. The number of vacant orbitals provided by central metal atom or ion is same as the co-ordination
number.
3. These vacant orbitals undergo hybridization to form same number of identical hybrid orbitals.
4. Each ligand has at least one orbital containing a pair of electron.
5. The empty hybrid orbitals of the metal ion overlap with the filled orbitals of the ligand to form
coordination covalent bond.
6. The geometrical shape of the complex ion depends on the type of hybridization of metal orbitals.

Co-ordination number Type of hybridization Geometry

4 sp3 Tetrahedral
4 dsp2 Square planar
5 dsp3 Trigonal bi-pyramidal
6 sp3d2 Octahedral
6 d2sp3 Octahedral

7. If (n-1)d-orbitals are used for hybridization, the complexes formed are called inner orbital complex.
When nd-orbitals are used for hybridization such complexes are called outer orbital complex.
8. When a complex contains one or more unpaired electrons it exhibits paramagnetic property. If no
unpaired electrons are present such a complex exhibit diamagnetic property.
APPLICATION OF VALENCE BOND THEORY:
1. hexaamminecobalt(III) ion: [Co(NH3)6]3+
In the given complex ion the central metal atom is cobalt whose electronic configuration in ground state
is [Ar] 3d7 4s2.
In this complex cobalt is in +3 oxidation state therefore electronic configuration is
3d 4s 4p
3+
Co = [Ar]  
Under the influence of strong field ligand NH3, the unpaired 3d electrons are forced to pair up in Co3+
against Hund’s rule of maximum multiplicity.
3d 4s 4p
3+
Co = [Ar]  
Now, two vacant 3d orbitals, one vacant 4s orbital and three vacant 4p orbitals combine together
forming d2sp3 hybridisation leading to formation of six hybrid orbitals.
3+
Co = [Ar]
2 3
d sp hybridisation  
Six pair of electrons, one from each NH3 ligand occupies the six vacant d2sp3 hybrid orbitals.
3+
[Co(NH3)6] = [Ar] xx xx xx xxxx xx
2 3
d sp hybridisation

Due to d2sp3 hybridization the complex ion acquires octahedral shape. There are no unpaired
electrons in the complex, hence diamagnetic. Since inner d-orbital (3d) are used in hybridization,
the complex is called inner orbital complex / spin paired complex/ Low spin complex.

2. hexafluoridocobaltate(III) ion: [CoF6]3-

In the given complex ion the central metal atom is cobalt whose electronic configuration in ground state
is [Ar] 3d7 4s2.
In this complex cobalt is in +3 oxidation state therefore electronic configuration is
3d 4s 4p 4d
3+
Co = [Ar]  
Under the influence of weak field ligand F-, the unpaired 3d electrons are not forced to pair up in Co3+
against Hund’s rule of maximum multiplicity. As a result outer d-orbitals participate in hybridization.
Now, one vacant 4s orbital three 4p orbitals and two 4d orbitals, hybridize to give six sp3d2 hybrid
orbitals.
3+
Co = [Ar]
3 2
3d sp d hybridisation 4d
-
Six pair of electrons one from each F ligand occupy the six vacant sp3d2 hybrid orbitals.
3-
[CoF6] = [Ar] xx xx xx xxxx xx
3 2
3d sp d hybridisation   4d
3 2
Due to sp d hybridization the complex ion acquires octahedral shape. There are four unpaired
electrons in the complex, hence paramagnetic. Since outer d-orbitals(4d) are used in hybridization,
the complex is called outer orbital complex / spin free complex / high spin complex.
3. tetrachloridonickelate(II) ion: [NiCl4]2-
In the given complex ion the central metal atom is nickel whose electronic configuration in ground state
is [Ar] 3d84s2
In this complex nickel is in +2 oxidation state therefore electronic configuration is
3d 4s 4p
2+
Ni = [Ar]

Under the influence of weak field ligand Cl-, the unpaired 3d electrons are not forced to pair up in Ni2+
against Hund’s rule of maximum multiplicity. As a result no d-orbital participate in hybridization. The
one vacant 4s orbital three 4p orbitals, hybridize to give four sp3 hybrid orbitals.
2+
Ni = [Ar]
3
sp hybridisation  
Four pair of electrons one from each Cl- ligand occupy the four vacant sp3 hybrid orbitals.
2-
[NiCl 4] = [Ar] xx xx xx xx
3
               sp hybridisation  
Due to sp3 hybridization the complex ion acquires tetrahedral shape. Since there are two unpaired
electrons in the complex it is paramagnetic in nature.

4. tetracyanidonickelate(II) ion: [Ni(CN)4]2-

In the given complex ion the central metal atom is nickel whose electronic configuration in ground state
is [Ar] 3d84s2
In this complex nickel is in +2 oxidation state therefore electronic configuration is
3d 4s 4p
2+
Ni = [Ar]  
 

Under the influence of strong field ligands like CN-, the unpaired 3d electrons are forced to pair up in
Ni2+ against Hund’s rule of maximum multiplicity. As a result one 3d-orbital becomes vacant.
3d 4s 4p
2+
Ni = [Ar]
Now, one vacant 3d orbital, one vacant 4s orbital and two vacant 4p orbitals hybridize to give four dsp2
hybrid orbitals.
3d 4p
2+
Ni = [Ar]
2
dsp hybridisation

Four pairs of electrons one from each CN- ligand occupy the four vacant dsp2 hybrid orbitals.
3d 4p
2-
[Ni(CN) 4] = [Ar] xx xx xx xx
2
dsp hybridisation  
Due to dsp2 hybridization the complex ion acquires a square planar in shape. There are no unpaired
electrons in the complex so it is diamagnetic. The complex is an inner orbital complex.
5. tetracarbonylnickel(0): [Ni(CO)4]
In the given complex the central metal atom is nickel whose electronic configuration in ground state is
[Ar] 3d84s2
In this complex nickel is in 0 oxidation state therefore electronic configuration is same as in ground
state.
3d 4s 4p
Ni = [Ar]
Under the influence of strong field ligand CO, the unpaired 3d electrons are forced to pair up in Ni
against Hund’s rule of maximum multiplicity. As a result one 3d-orbital becomes vacant. Further the
pair of electron present in 4s orbital shifts to the vacant 3d orbital giving the configuration.
3d 4s 4p
Ni = [Ar]

Now, one vacant 4s orbital and three vacant 4p orbitals hybridize to give four sp3 hybrid orbitals.
Ni = [Ar]
3
sp hybridisation
Four pairs of electrons one from each CO ligand occupy the four vacant sp3 hybrid orbitals.
[Ni(CO)4] = [Ar] xx xx xx xx
                  
3
Due to sp hybridization, the complex acquires tetrahedral shape. There are no unpaired electrons
in the complex, so it is diamagnetic.

MAGNETIC PROPERTIES OF CO-ORDINATION COMPOUNDS:

Magnetic moment of co-ordination compounds can be measured by using magnetic susceptibility
experiment. The results can be used to explain the structures adopted by metal complexes.

Case I: In case of metal ions containing d1, d2, d3 configuration.

Example: Sc2+ has got configuration of [Ar] 3d1.

Ti2+ has got configuration of [Ar] 3d2.
V2+ has got configuration of [Ar] 3d3.

, ,
2+ 2+ 2+
Sc Ti V
In all these ions, two vacant d-orbitals are available for d2sp3 hybridization with 4s and 4p orbitals. The
magnetic behavior of these free ions and their coordination entity is similar irrespective of the strength
of the ligand.

Case II: In case of metal ions with more than three electrons in their d orbitals-
When more than three, d-electrons are present, then the required pair of 3d orbitals for octahedral
hybridization is not directly available because all the degenerate orbitals are singly occupied with
electrons before pairing occurs. Thus in d4(Cr2+, Mn3+), d5(Mn+2, Fe3+), d6(Fe2+, Co3+) cases, a pair of
vacant d-orbitals result only by pairing of 3d electrons which leaves two, one and zero unpaired
electrons respectively.
 3d 4s 4p
2+ 3+
Cr , Mn
before pairing
3d 4s 4p
2+ 3+
Cr , Mn
2 3
d sp hyb. after pairing  
3d 4s 4p
2+ 3+
Mn , Fe
before pairing
3d 4s 4p
2+ 3+
Mn , Fe
2 3
d sp hyb. after pairing  
3d 4s 4p
2+ 3+
Fe , Co
before pairing
3d 4s 4p
2+ 3+
Fe , Co
2 3
d sp hyb. after pairing
 
This type of pairing takes place in the presence of strong field ligands resulting in the formation of
inner orbital complex with d2sp3 hybridization.
In case of weak field ligands, the pairing does not take place, therefore outer orbital complex are
formed with sp3d2 hybridization.

Examples:
Case-1: [Mn(CN)6]3- has magnetic moment corresponding to two unpaired electrons while [MnCl6]3-
has magnetic moment corresponding to four unpaired electrons. (CN- is a strong field ligand and Cl-
is a weak field ligand)
Case-2: [Fe(CN)6]3- has magnetic moment corresponding to a one unpaired electron while [Fe F6]3-
- -
has magnetic moment corresponding to five unpaired electrons. (CN is a strong field ligand and F
is a weak field ligand)
Case-3: [Co F6]3- is magnetic with four unpaired electrons while [Co(C2O4)3]3- is diamagnetic since
No unpaired electrons.

LIMITATIONS OF VBT:
1) It involves number of assumptions.
2) It does not explain the colour exhibited by co-ordination compounds.
3) It fails to explain thermodynamic and kinetic stability of co-ordination compounds.
4) It does not distinguish between strong field and weak field ligands.
5) It does not make exact prediction regarding tetrahedral and square planar structure of co-
ordination complexes with co-ordination number 4.

CRYSTAL FIELD THEORY: (CFT) The crystal field theory was developed by H.Bethe and Vleck.
According to CFT,
1. The metal-ligand bond is ionic arising from electrostatic interactions between metal ion and
ligands. The ligands are treated as point charges.
2. In case of negative ligands (anion such as CN-, Cl- etc.) the interaction with metal ion is ion-ion
interaction.
3. In case of neutral ligands (CO, H2O etc..) the interaction with metal ion is ion-dipole interaction.
SPLITTING OF ENERGY LEVELS:
The d orbitals are divided into two groups based on their orientation in space. Three orbitals are
oriented between the axis (dxy, dyz, dzx) while the other two are oriented along the axis.
(dx2- y2 , dz2).
X Y X

Y Z Z

dxy dyz dzx  

X Z

Y Y

2 2 2
dx - y dz
 In the case of free metal atom or ion, all the five d orbitals have same energy. The orbitals having
the same energy are called degenerate orbitals.
 On the approach of ligands, the d-electrons of central metal atom /ion will be repelled by the lone
pair electrons or negative charge of the ligand. This repulsion will raise the energy of the d-orbitals.
If all the ligands approach the central metal atom or ion at equal distance, the energy of each orbital
will increase by the same amount due to symmetrical field of ligands. Therefore these orbitals will
still remain degenerate but they have higher energy than that of free ion.
 But we know that d-orbitals differ in their orientations. The orbitals lying along the axis in the
direction of ligands will have greater repulsion and their energies will be raised to a larger extent
than that of the orbitals lying in between the axis. Therefore, due to the electric field of ligands, the
energies of five d-orbitals will split up in to two set of orbitals, thus the degeneracy is lost.

CRYSTAL FIELD SPLITTING:

Splitting of the five degenerate d-orbitals of the central metal into different sets of orbitals
having different energies in the presence of ligands is called crystal field splitting.

CRYSTAL FIELD SPLITTING IN OCTAHEDRAL COMPLEXES:

 During the formation of octahedral complexes, the six ligands approach the central metal atom/ion
along the axis.
 The two d-orbitals namely dx2 – y2 and dz2 that lie along the axis will experience greater repulsion
between the electrons present in them and the electrons of ligands. As a result dx2 – y2 and dz2
orbitals will be raised in energy while the electrons present in dxy, dyz, dzx orbitals which are directed
between the axes will experience less repulsion and are thus lowered in energy.
 Hence the degeneracy of d-orbitals gets disturbed and thus d- orbitals split into two sets of different
energies. One set of lower energy called t2g set (dxy, dyz, dzx) and the other set of higher energy
called eg set (dx2 – y2 and dz2).
 2 2 2
dx -y dz (e g orbitals)
-------------- --------------

3 
5

ENERGY

2 
av erage energy of the 5
d-orbital in a spherical -------------- --------------
cry stal f ield
dxy dy z dzx (t 2g orbitals)

d-orbital in f ree splitting of d-orbital

metal ion

CRYSTAL FIELD SPLITTING ENERGY:

The energy difference between two sets of t2g and eg orbitals is called crystal field splitting
energy and is represented as ∆o (subscript ‘o’ stands for octahedral).
The energy of the two eg orbitals will be increased by 3/5 ∆o and that of three t2g orbitals will be
decreased by 2/5 ∆o.

SPECTRO CHEMICAL SERIES:

The crystal field splitting depends on the field strength produced by the ligand and charge on the
metal ion.
The ligands which cause a large crystal field splitting are called strong field ligands and those
which cause small crystal field splitting are called weak field ligands.

Arrangement of ligands in the increasing order of crystal field splitting energy or increasing
field strength is called spectro chemical series.
I-< Br-< SCN-< Cl-< S2-< F-< OH-< C2O42-< H2O< NCS-< edta4-< NH3< en< CN-< CO
Above series is an experimentally determined series based on the absorption of light by complex with
different ligands. In general, the ligands lying after H2O are called strong field ligands and they
cause greater crystal field splitting and the ligands lying before H2O are called weak field ligands
and they cause lesser crystal field splitting.

ASSIGNMENT OF ELECTRONS IN THE d-ORBITALS IN CO-ORDINATION COMPLEXES:

In d1 configuration, the single d-electron occupies one of the t2g orbital. Similarly in d2 and d3
configuration also the electrons occupy t2g orbitals according to Hund’s rule.

eg
E
t2g
1 2 3
d complex d complex d complex
1 0 2 0 3 0
t 2g e g t 2g e g t 2g e g
 
In d4 system two possibilities are:
 All the four electrons may occupy t2g orbitals. The electronic configuration is t2g4 eg0. In this case, one
of the t2g orbital is completely filled and the other two are half filled.
 Three electrons occupy t2g orbital and the fourth electron goes to one of the eg orbitals. The
electronic configuration is t2g3 eg1.
The actual configuration depends upon the magnitude of ∆o and pairing energy. (pairing energy is the
energy required to pair the electrons in a single orbital).

1. If ∆o > P, pairing is favorable that is the fourth electron will enter into t2g orbital with electronic
configuration t2g4 eg0. The ligands that produce this effect are known as strong field ligands and the
complex formed is a low spin complex.

2. If ∆o < P, pairing is difficult so fourth electron will enter into one of the eg orbital with electronic
configuration t2g3 eg1. The ligands that produce this effect are known as weak field ligands and the
complex formed is a high spin complex.

Example: [CoF6]3- and [Co(CN)6]3- are both octahedral complex of cobalt in +3 oxidation state and it
has six d-electrons. F- Ion being a weak field ligand and therefore ∆o is small. The complex will be a
high spin complex while CN- ion being a strong field ligand and therefore ∆o is high, the electrons will
pair up and lead to low spin complex.

eg
eg
 high
E  small

t 2g t 2g
6 0 4 2
t 2 eg t 2 eg
strong f ield ligand week f ield ligand
(low spin complex) (high spin complex)  
 

CRYSTAL FIELD SPLITTING IN TETRAHEDRAL COMPLEXES:

During the formation of tetrahedral complexes, the three d-orbitals dxy, dyz and dzx are close to the
approaching ligands. While the other two d orbitals dx2 – y2, dz2 lying in between the axis are far from the
approaching ligands. So the energy of three orbitals will be raised and the other two orbitals will be
lowered.
dxy dyz dzx (t 2 orbitals)
-------------- -- ---- ---- ----

2 
t
5
ENERGY

----------------------------  t
3
av erage energy of the t
5
d-orbital in a spherical
cry stal f ield -------------- --------------

2 2 2
dx -y dz (e orbitals)
d-orbital in f ree
splitting of d-orbital
metal ion  

The energy difference between the two sets (t2 and e) is called crystal field splitting energy and is
represented as ∆t
Thus, each t 2 orbital is raised in energy by 2/5 ∆t and each e orbitals is lowered in energy by 3/5 ∆t.
Note:
The splitting in tetrahedral complexes is considerably less than in octahedral complexes. It has been
found that ∆t = (4/9) ∆O
COLOUR IN COORDINATION COMPOUNDS:
Transition metal complexes exhibit colour because during the d-d electron transition from t2g to eg or
e to t2 orbitals, a certain wavelength of visible spectrum is absorbed. The wavelength left unabsorbed
give specific colour to the complex. The colour of the complex observed is complementary to the colour
absorbed.
If green light is absorbed, then complex appears red. Red is complementary colour to green.
Example: In [Ti(H2O)6]3+, Ti3+ is in +3 oxidation state. It is 3d1 system. The configuration is t2g1eg0. To
cross the energy gap, the electron in t2g orbital absorbs blue-green region of VIBGYOR. The
configuration changes as t2g0 eg1. The complex appears violet in colour.

eg eg

h
 
E

t 2g t 2g
1 0 0 1
t 2 eg t 2 eg
 
It is important to note that in the absence of ligand, crystal field splitting does not occur hence the
substance is colourless.
The crystal field splitting is more in the presence of stronger ligands than a weaker ligand. For the
same metal, the crystal field splitting is more in higher oxidation state than in lower oxidation state. The
crystal field splitting is higher in the octahedral complexes than in tetrahedral complexes.

COLOUR OF SOME COORDINATION COMPOUNDS:

Wavelength of light Colour of light Colour of the
Coordination entity
absorbed (nm) absorbed coordination entity
[Co(NH3)5Cl]2+ 535 yellow Violet
[Co(NH3)5(H2O)]3+ 500 Green Red
[Co(NH3)6]3+ 475 Blue Orange
[Co(CN)6]3- 310 Ultra violet Pale yellow
[Co(H2O)4]2+ 600 Orange Blue
[Ti(H2O)6]3+ 498 Blue green Purple

The influence of the ligand on the colour of a complex may be illustrated by considering the [Ni(H2O)6]2+
complex, which forms when nickel(II) chloride is dissolved in water. If the didentate ligand, ethane-1,2-
diamine(en) is progressively added in the molar ratios en:Ni, 1:1, 2:1, 3:1, the following series of
reactions and their associated colour changes occur.
[Ni(H2O)6]2+(aq) + en (aq) [Ni(H2O)4(en)]2+(aq) + 2H2O
Green pale blue
[Ni(H2O)4(en)]2+(aq) + en (aq) [Ni(H2O)2(en)2]2+(aq) + 2H2O
pale blue blue/purple

[Ni(H2O)2(en)2]2+(aq) + en (aq) [Ni(en)3]2+(aq) + 2H2O

blue/purple violet
METAL CARBONYLS:
Metal carbonyls are homoleptic complexes in which carbonyl ligands are linked to the central metal
atom by coordinate bonds. In these coordination compounds, the oxidation state of metal atom is zero.
Metal carbonyls are of two types:

1. MONONUCLEAR CARBONYLS: In mononuclear carbonyls only one metal atom is present per
molecule. 
Examples: 
 

CO CO CO

CO OC CO
Ni OC Fe
CO Cr
OC CO OC CO
CO

CO CO
[Ni(CO) 4] [Fe(CO) 5] [Cr(CO) 6]
Tetrahedral Trigonal bipyramidal Octahedral  
 

2. POLYNUCLEAR CARBONYLS: In polynuclear carbonyls, two metal atoms is present per molecule. 
Examples:
O
CO CO
CO CO OC C CO

OC Mn Mn CO OC Co Co CO

OC OC C CO
OC
CO CO O
[Mn2(CO) 10] [Co 2(CO) 8]  

BONDING IN METAL CARBONYLS:

Metal carbon bond in metal carbonyls has σ character and π character. The metal-carbonyl σ bond is
formed by the donation of lone pair of electrons on carbon of carbonyl ligand in to the vacant orbital of
metal. The vacant antibonding π molecular orbitals overlap with the filled d-orbitals on the metal atom
to form a metal carbon π bond. Thus M to C bond in metal carbonyls consists of a weak C  M sigma
bond and M  C pi bond which results due to back-bonding. The back bonding between metal to
carbon creates a synergic effect which stabilises the M to C bond.
*


 O
M C

Bonding in metal carbonyl

IMPORTANCE OF COORDINATION COMPOUNDS:

1. IN QUALITATIVE ANALYSIS AND QUANTITATIVE ANALYSIS:
Coordination compounds find use in many qualitative and quantitative chemical analyses. The familiar
colour reactions given by metal ions with a number of ligands (especially chelating ligands), as a result
of formation of coordination entities, form the basis for their detection and estimation by classical and
instrumental methods of analysis.
Examples of such reagents include EDTA, DMG (dimethylglyoxime), α–nitroso–β–naphthol, cupron,
etc.
2. ESTIMATION OF HARDNESS OF WATER:
Hardness of water is estimated by simple titration with Na2EDTA. The Ca2+ and Mg2+ ions form stable
complexes with EDTA. The selective estimation of these ions can be done due to difference in the
stability constants of calcium and magnesium complexes.

3. IN METALLURGICAL PROCESSES:
Complex formation technique are also used for the extraction of metals such as gold and silver
Example: silver is extracted from its ores by the cyanide process. In this process, silver passes into
solution with formation of complex Na[Ag(CN)2]

Ag2S + 4NaCN 2Na[Ag(CN)2] + Na2S

The solution containing the silver complex is removed and treated with zinc dust.

2Na[Ag(CN)2] + Zn Na2[Zn(CN)4] + 2Ag

4. BIOLOGICAL IMPORTANCE:
Many biological important natural compounds exist as coordinate complexes.
Chlorophyll: The green pigments in plants, which helps for photosynthesis is a complex compound of
Mg2+
Hemoglobin: The red pigments of blood which acts as oxygen carrier is a complex compound of Fe2+
Vitamin B12: This is chemically cyanocobalamine, the anti-pernicious anaemia factor, is a
coordination compound of Co3+.
All these are the coordination compounds with macrocyclic porphyrin and coorrin ligands. Other
biological importance with coordinated metal ions are the enzymes like, carboxypeptidase A and
carbonic anhydrase (catalysts of biological systems).

5. IN CATALYSIS:
Coordination compounds acts as catalysts for different reactions.
Examples: [(Ph3P)3RhCl], a Wilkinson catalyst, is used for the hydrogenation of alkenes.

6. IN ELECTROPLATING:
Articles can be electroplated with silver and gold much more smoothly and evenly from solutions of the
- -
complexes, [Ag(CN)2] and [Au(CN)2] than from a solution of simple metal ions.

7. IN MEDICINES:
Many coordination compounds are used in medicines. These are involved in chelate formation and the
treatment is often called chelate therapy.
Examples:
 Cis-[Pt(NH3)2Cl2] is known as cis platin used in cancer therapy.
 Calcium salt of EDTA is used in the treatment of lead poisoning. In human body, calcium in the
complex is replaced by lead. Lead-EDTA complex is eliminated in urine.
 The presence of metals in toxic proportions in plant or animal systems. Thus, excess of copper and
iron are removed by the chelating ligands D–penicillamine and desferrioxime B via the formation of
coordination compounds.
*********