CHAPTER: 5 COORDINATION COMPOUNDS

INTRODUCTION:
These are the class of compounds in which a metal atom / metal ion forms compounds with
electron rich species by means of co–ordinate covalent bonds.

Coordination compounds are the inorganic salts formed by the combination of two or more
simple salts in stoichiometric ratio.
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 (blood).
 Cryolite is an aluminum complex present in minerals.

TYPES OF INORGANIC SALTS:

1. SIMPLE SALTS:
The compounds made up of one acidic 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- Cuprammonium sulphate

DIFFERENCE BETWEEN DOUBLE SALTS AND COMPLEX COMPOUNDS:

Double salts Complex salt

1. Contains two simple salts Contains at least one complex ion
2. They dissociate into all ions They dissociate in solution to complex
present in the salt in solution. cation or complex anion or both complex
cation and complex anion.
3. They answer the test for all They answer the test for complex ion and
ions in solution simple ion present in solution
4. They are formed by ionic They are formed by co – ordinate
bonds. covalent bonds.
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 carrying positive charge on its complex part is called a cationic complex.
Examples: [Co(NH3)6]3+, [Ni(NH3)6]2+ etc..

b. ANIONIC COMPLEX:
A coordination compound carrying negative charge on its complex part is called an anionic complex.
Examples: [Fe(CN)6]4-, [Ag(CN)2]1- etc..

c. NEUTRAL COMPLEX:
A coordination compound carrying no charge on its complex part entity is called a neutral complex.
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 atom / 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 atom / ion/ molecule bonded to the central metal atom / ion through a co-ordinate bond in the
coordination entity are called as ligands.

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

Note: In all the coordination compounds, central metals 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 or ion,
ligands are of the following types.

a. 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.
NEUTRAL LIGANDS: H2O, NH3, NO, CO, C5H5N, etc…
 - - - - - -
ANIONIC LIGANDS: CN , Cl , OH , NO2 , NO3 , ONO , etc...

b. BI-DENTATE LIGANDS:
Ligands which coordinate with the central metal atom or ion through two donor atoms are called as
bidentate ligands.
Examples: SO42-, CO32-,
- .. ..
COO CH 2NH 2 CH 3- C=N-OH
- .. .. .. -
COO CH 2NH 2 CH 3- C=N-OH H2N-CH 2-COO
oxalate ion(ox) Ethane-1,2-diamine(en) dimethyl glyoxime(dmg) glycinate ion
Note:
The bidentate ligands in which two ligating atoms are the same are called symmetrical
bi-dentate ligands.
Example: oxalate ion, ethane-1,2-diamine, dimethyl glyoxime.

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

c. 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-CH 2-CH 2-NH-CH 2-CH 2-NH 2
diethylene triamine

II. TETRA DENTATE LIGANDS: Ligands which can coordinate to the central atom through four donor atoms.
Examples:
.. .. .. ..
H2N-CH 2-CH 2-NH-CH 2-CH 2-NH-CH 2-CH 2-NH 2
triethylene tetraamine

III. PENTA DENTATE LIGANDS: Ligands which can coordinate to the central atom through five donor atoms.
Examples: _
_ .. .. COO
OOC-NH-CH 2-CH 2-N _
COO
ethylenediaminetriacetate ion

IV. HEXA DENTATE LIGANDS: Ligands which can coordinate to the central atom through six donor atoms.
Examples:
_ _
OOC .. .. COO
_ N-CH 2-CH 2-N _
OOC COO
4-
ethylenediaminetetraacetate ion (edta)

AMBIDENTATE LIGANDS:
The mono dentate ligands which can coordinate to the central metal atom through more than one donor
site at a time are called Ambidentate ligands.
Example: NO2 can coordinate to the metal atom through nitrogen or oxygen.
 M O-NO M NO 2
Nitrito-O (Nitrito) Nitrito-N (Nitro)

M CN M NC
Cyanido Isocyanido

M SCN M NCS
Thiocyanato Isothiocyanato

The following tables will give the list of all types of ligands. The table consists of formula or
structure, name of the ligand, abbreviation if any, the term used in IUPAC nomenclature for the
ligand and charge on the ligand.
Neutral monodentate ligand:
Structure or Common Abbreviations IUPAC name of the Charge
formula name of the if any ligand on the
ligand ligand
Ammonia - ammine 0
Water - aqua 0
Pyridine py pyridyl 0

C5H5N
Triphenyl - triphenylamine 0
amine
Phosphine - phosphine 0
Triphenyl - triphenylphosphine 0
phosphine
Nitric oxide - nitrosyl 0
CO Carbon - carbonyl 0
monoxide
Ethyl amine - ethanamine 0

List of negative mono dentate ligands:

CN– Cyanide* - cyanido –1

NO 2 Nitrite ion* - nitrito–O– or nitrito–N– –1
NO3 Nitrate ion - nitrato –1
SCN– Thiocyanide* - thiocyanato –1
CH3COO– Acetate - acetate –1
F– Fluoride - fluorido –1
Cl– Chloride - chlorido –1
Br– Bromide - bromido –1
I– Iodide - iodido –1
OH– Hydroxide - hydroxido –1
CO32 Carbonate - carbonato –2
 SO 32  Sulphite - sulphito –2
SO 24  Sulhate - sulphato –2
S2– Sulphide - sulphido –2
O2– Oxide - oxido –2
PO 34 Phosphate - phosphato –3

List of positive monodentate ligand:

NO+ Nitrosonium - nitosonium +1

NO 2 Nitronium - nitronium +1
H 2 N - NH 3 Hydrazinium - hydrazinium +1

List of neutral bidentate ligand:

Ethylenediamine en ethylenediamine or 0
ethane–1,2–diamine

bipyridyl bipy bipyridyl 0

1,10–phenanthrolein o–phen 1,10–phenanthrolein 0

List of negative bidentate ligands:

Oxalate ox Oxalato –2

Glycinate gly glycinato –1

dimethylglyoxime dmg dimethylglyoxamato –1

List of tridentate lgand:
diethylenetriamine dien diethylenetriamine 0

2,2–6|,2||– terpyridine terpy 2,2–6|,2||– terpyridyl 0

Example of tetradentate ligand:

triethylenetetraamine trien triethylenetetraamine 0

Example for pentadentate ligand:

ethylenediaminetriacetate EDTA3 ethylenediaminetriacetato –3

Example for hexadentate ligand:

Ethylenediaminetetraacetate EDTA ethylenediaminetetraacetato –4
CHELATION:
When a di or poly dentate ligand uses its two or more donor atoms to bind to the same central metal
atom or ion is called chelation.
The resulting complex has ring structure and the ligand coordinating through two or more donor groups is called
chelating ligand.
Example:
.. .. .. 2+
CH 2-H 2N CH 2-H 2N NH 2-CH 2
.. .. Cu ..
CH2-H2N CH2-H2N NH2-CH 2
Chelating ligand Chelate complex

DENTICITY:
The number of ligating atoms present n 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
4-
Denticity of ethylene diamine tetraacetate (edta) 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.
EFFECTIVE ATOMIC NUMBER (EAN):
Sidwick has calculated the EAN of the metal atom or ion in the co-ordination complex by using the following
equation.

EAN = Atomic no. of metal atom - Oxidation state of metal ion + 2 x Coordination no.
In some cases, EAN coincides with the atomic number of the nearest noble gas element according to Sidwick, if it
happens the co-ordination complex is expected to be quite stable.

Complex Oxidation Atomic number of Coordination

EAN
compound state central metal ion number

K4[Fe(CN)6] +2 26 6 36

K3[Fe(CN)6] +3 26 6 35

[Co(NH3)6]Cl3 +3 27 6 35

[Cu(NH3)4]SO4 +2 29 4 35

K2[Pt(Cl)6] +4 78 6 86

[Ag(NH3)2]Cl +1 47 2 50

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 ionic complexes, 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 ligands: Different types of ligands are named as.
 Negatively charged ligands are named ending with ‘O’.
Examples:
Symbol Name as ligand Symbol Name as ligand
-
F- fluorido SCN thiocyanato
-
Cl- chlorido NCS Isothiocyanato
Br- bromido (COO)22- Oxalato
NO2- nitrito-N CO32- carbonato
-
ONO nitrito-O NO3- nitrato
SO42- sulphato CN -
cyanido
-
OH hydroxo NH2- amido

 Neutral ligands are named as follows:

Examples:

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 NH2CH2CH2NH2 ethane-1,2-diamine(en)

 Positively charged ligands are named ending with ‘ium’.

Examples: NO2+ – nitronium, NO+ - nitrosonium, NH2NH3+ - hydrazinium

3. 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)

4. NAMING THE COMPLEX ION:

 Positive complex ion: If the complex entity is a positive ion, it is named starting from the ligands followed by
the name of the metal ion as such.
 Negative complex ion: If the complex entity is negative, it is named starting from the ligands followed by the
name of the metal ion. However the name of metal ends with ‘ate’.
Latin names of certain metals:

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

 Neutral complex ion: If the complex entity is neutral, it is named similar to that of positive complex ion.
5. ALPHABETICAL ORDER: If two or more different types of ligands they are named in the alphabetical order of
their names.
Example: chloride and ammine groups are named as amminechlorido.
ammine and aqua ligands are named as ammineaqua.

6. PREFIX OF LIGANDS: Two or more identical ligands are named using the prefix di, tri, tetra, penta etc…
7. If the name of the ligand itself contains a prefix, the ligands are named using prefixes like bis(2), tris(3),
tetrakis(4), pentakis(5), etc..
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 tetramminecopper(II) sulphate
3 [Cr(H2O) 4Cl2]NO3 tetraaquadichloridochromium(III) nitrate
4 [Cr(H2O)6]Cl3 hexaaquachromium(III) chloride
5 [Pt (NH3)2 Cl2] diamminedichloridoplatinum(II)
6 [PtCl2(NH3)4NO2]2SO4 tetraamminedichloridonitrito-N-platinum(V) sulphate
7 [Pt (NH3)4Cl2]Br2 tetraamminedichloridoplatinum(IV) bromide
8 [Co(NH3)6]Cl3 hexaamminecobalt(III) chloride
9 [Co(NH3)3(NO2)3] triamminetrinitrito-N-cobalt(III)
10 [Ni(dmg)2] dimethylglyoximatonickel(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(NCS)4] ammonium diamminetetrathiocyanato-N-chromate(III)
19 K3[Fe(C2O4)3] potassium trioxalatoferrate(III)
20 Na2[Ni(edta)] sodium ethylenediaminetetraacetatonickelate(II)
21 [Cu(H2O)2(NH3)4]SO4 tetraamminediaquacopper(II) sulphate

22 [Ni(CO)4] tetracarbonylnickel(0)
23 [Pt(NH3)4][PtCl4] tetraamineplatinum(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 symbols of metal atom/ ion and ligands are represented in the co-ordination sphere without any gap.
7. The alphabetical order should be considered only by the names of the ligand and not by the prefixes used for
ligands.
8. 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)
9. 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

Examples of IUPAC names to formula of compounds:

tetraammineaquachloridocobalt(III) chloride [CoCl(NH3)4(H2O)]Cl2
potassium tetrahydroxidozincate(II) K2[Zn(OH)4]
potassium trioxalatoaluminate(III) K3[Al(C2O4)3]
dichloridobis(ethane-1,2-diamine)cobalt(III) [CoCl2(en)2]+
tetracarbonylnickel(0) [Ni(CO)4]
hexaamminecobalt(III) sulphate [Co(NH3)6]2(SO4)3
potassium tri(oxalato)chromate(III) K3[Cr(C2O4)3]
hexaammineplatinum(IV) [Pt(NH3)6]4+
potassium tetracyanidonickelate(II) K2[Ni(CN)4]
tetrabromidocuprate(II) [CuBr4]2–
Pentaamminenitrito–O–cobalt(III) [Co(NH3)5(ONO)]2+
Pentaamminenitrito–N–cobalt(III) [Co(NH3)5(NO2)]2+
potassium tetrachloridopalladate(II) K2[PdCl4]
diamminedichloridoplatinum(II) [Pt(NH3)2Cl2]

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:
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]SO4 [Co(NH 3)5Br] + SO4
pentamminebromidocobalt(III) sulphate gives white ppt with
(red violet) Barium chloride

+ -
[Co(NH 3)5SO4]Br [Co(NH 3)5SO4] + Br
pentamminesulphatocobalt(III) bromide gives pale yellow ppt with
(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 NO 2 . 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 AgNO 3 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]BrH2O
[Co(H2O)Cl(en)2]Cl2 and [CoCl2(en)2]ClH2O

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 [PtCl 2(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]

.---------------... 3 .---------------...Cl
Cl . NH H 3N .
... .. ... ..
.. Pt .. ... Pt ...
... ... .. .
.
Cl ---------------.
.--------------- .. NH3
NH3 Cl
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
H2 C .. .
.. O=C .. .
..
... Pt .
.
CH2 ... Pt .
.
CH2
O=C .. . . H2C .. . .
. .. C=O . .. 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], [M(aa)b2] [M(a2b2c2)]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

BONDING IN CO-ORDINATION COMPOUNDS:

Alfred Werner was the first to describe the bonding features in coordination compounds. But his theory
could not answer basic questions like:
i. Why only certain elements possess the remarkable property of forming coordination compounds?
ii. Why the bonds in coordination compounds have directional properties?
iii. Why coordination compounds have characteristic magnetic and optical properties?
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). We shall focus our attention on elementary treatment of the application of VBT and CFT to
coordination compounds.
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 (LIMITATION’S) 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.

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 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 hybridization of the metal orbitals.

Co-ordination Type of hybridization Geometry

number
4 sp3 Tetrahedral
2
4 dsp Square planar
3
5 dsp Trigonal bi-pyramidal
3 2
6 sp d Octahedral
2 3
6 d sp Octahedral

7. If (n-1)d-orbitals are used for hybridization the complexes 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.
9. The paramagnetic nature of the compound can be measured by measuring spin only
magnetic moment as   n(n  2) BM (bohrmagneton), where n is the number of unpaired
electrons.

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 ligands like 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
2 3
d sp hybridisation
Six pair of electrons, one from each NH3 ligand occupies the six vacant d2sp3 hybrid orbitals.
3+ xx xx xx xxxx xx
[Co(NH 3)6]
2 3
d sp hybridisation

Due to d2sp3 hybridization the complex ion acquires an octahedral shape. There are no unpaired electrons in
their complex, so it is 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 Co3+
3d 4s 4p 4d
3+
Co

Under the influence of weak field ligands like 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
3 2
3d sp d hybridisation 4d
-
Six pair of electrons one from each F ligand occupy the six vacant sp3d2 hybrid orbitals.
3-
[CoF 6] xx xx xx xxxx xx
3 2
3d sp d hybridisation 4d
3 2
Due to sp d hybridization the complex ion acquires an octahedral shape. There are four unpaired electrons
in this complex, so it is 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]183d84s2
In this complex nickel is in +2 oxidation state therefore electronic configuration is
3d 4s 4p
2+
Ni
-
Under the influence of weak field ligands like 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
3
sp hybridisation
-
Four pair of electrons one from each Cl ligand occupy the four vacant sp3 hybrid orbitals.
2-
[NiCl 4] 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]183d84s2
In this complex nickel is in +2 oxidation state therefore electronic configuration is
3d 4s 4p
2+
Ni

-
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
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
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] 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]183d84s2
In this complex nickel is in 0 oxidation state therefore electronic configuration is same as in ground state.
3d 4s 4p
Ni
Under the influence of strong field ligands like 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

Now, one vacant 4s orbital and three vacant 4p orbitals hybridize to give four sp3 hybrid orbitals.

Ni
3
sp hybridisation
Four pairs of electrons one from each CO ligand occupy the four vacant sp3 hybrid orbitals.
[Ni(CO) 4] xx xx xx xx

Due to sp3 hybridization, the complex acquires a tetrahedral in shape. There are no unpaired electrons in this
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 information about 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]183d1.

Ti2+ has got configuration of [Ar]183d2.
V2+ has got configuration of [Ar]18 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 paramagnetic moment corresponding to two unpaired electrons while [MnCl6]3- has
- -
paramagnetic 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 paramagnetic moment corresponding to a one unpaired electron while [Fe F6]3- has
- -
paramagnetic 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 paramagnetic with four unpaired electrons while [Co(C2O4)3]3- is diamagnetic since No
unpaired electrons.

LIMITATIONS OF VBT:
1) It involves a number of assumptions.
2) It does not explain the colour exhibited by co-ordination compounds.
3) It fails to explain thermodynamics 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 [Link] and [Link].
According to CFT,
1. The metal-ligand bond is ionic arising from electrostatic interactions between metal ion and ligands.
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 (d xy, dyz, dzx) while the other two are oriented along the axis
(dx2- y2 , dz2).

 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 orbital 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 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 metal ion into different sets of orbitals having different
energies in the presence of ligands is called crystal field splitting.

CRYSTAL FIELD SPLITTING IN OF d- ORBITALS 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 d x2 – 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 e g set (dx2 – y2 and
dz2).

2 2 2
dx -y dz (eg orbitals)
-------------- --------------

3 
ENERGY

5

--------------------------------------------------
2 
av erage energy of the 5
d-orbital in a spherical
-------------- --------------
cry stal f ield
dxy dyz dzx (t2g orbitals)
d-orbital in f ree
metal ion splitting of d-orbital

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 or 6 Dq and that of three t2g orbitals will be
decreased by 2/5 ∆o or 4 Dq.
SPECTRO CHEMICAL SERIES:
The crystal field splitting depends on the field 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.
- - - - 2- - - 2- - 4- -
I < Br < SCN < Cl < S < F < OH < C2O4 < H2O< NCS < edta < 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

t 2g
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. (It is the energy required for
electron pairing 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
 hig h
 small

t2g t2g
4 0 3 1
t 2 eg t 2 eg
strong field ligand week field 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 d x2 – 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 (t2 orbitals)

-------------- -- -- -- -- -- -- --

2
t
5
t
ENERGY

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

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

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 or 4 Dq and each e orbitals is lowered in energy by 3/5 ∆ t or
6Dq.

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 nature 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 a green light is absorbed, then complex looks red. Red is complementary 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
 

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 than in lower oxidation state. The crystal field splitting is
higher in the octahedral complexes than in tetrahedral complexes.
COLOUR OF SOME COORDINATION ENTITIES:
Wavelength of light Colour of light Colour of the
Coordination entity
absorbed (nm) absorbed coordination entity
[CoCl(NH3)5]2+ 535 yellow Violet
3+
[Co(NH3)5(H2O)] 500 Green Red
3+
[Co(NH3)6] 475 Blue Orange
3-
[Co(CN)6] 310 Ultra violet Pale yellow
2+
[Co(H2O)4] 600 Orange Blue
3+
[Ti(H2O)6] 498 Blue green Purple

The influence of the ligand on the colour of a complex may be illustrated by considering the [Ni(H 2O)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 is linked to the central metal atom by
coordinate bonds. In these coordination compounds, the oxidation 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 Cr
CO
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:
CO CO CO CO
CO CO OC CO

OC Mn Mn CO Co Co

OC OC OC CO
CO CO OC CO

[Mn2(CO) 10] [Co2(CO) 8]

STABILITY OF COORDINATION COMPLEXES:
The stability of a complex in solution refers to the degree of association between the two species involved in the
state of equilibrium. The magnitude of the (stability or formation) equilibrium constant for the association,
quantitatively expresses the stability.
Thus, if we have a reaction of the type:

M + 4L ML4

The larger the stability constant, the higher the proportion of ML 4 that exists in solution. Free metal ions rarely
exist in the solution so that M will usually be surrounded by solvent molecules which will compete with the ligand
molecules L, and be successively replaced by them. For simplicity, we generally ignore these solvent molecules
and write four stability constants as follows:

M+L ML k1 = [ML] / [M] [L]

ML + L ML2 k2 = [ML2] / [ML] [L]

ML2 + L ML3 k3 = [ML3] / [ML2] [L]

ML3 + L ML4 k4 = [ML4] / [ML3][ L]

Where K1, K2, etc., are referred to as stepwise stability constants.

Alternatively, we can write the overall stability constant thus:
M + 4L ML4 β4 = [ML4] / [M][L]4
The stepwise and overall stability constant are therefore related as follows:
β4 = k1 × k2 × k3 × k4 or more generally,
βn = k1 × k2 × k=× k4 ....... kn

Example: The steps involved in the formation of the cuprammonium ion, we have the following:
Cu2+ + NH3 [Cu(NH3)]2+ k1 = [Cu(NH3)2+] / [Cu2+] [NH3]
[Cu(NH3)]2+ + NH3 [Cu(NH3)2]2+ k2 = [Cu(NH3)2 2+] / [Cu(NH3)]2+ [NH3] etc.
Where k1, k2 are the stepwise stability constants and overall stability constant.
Also β4 = [Cu(NH3)4] 2+] / [Cu2+][NH3]4
The addition of the four amine groups to copper shows a pattern found for most formation constants, in that the
successive stability constants decrease.
In this case, the four constants are:
logk1 = 4.0, logk2 = 3.2, logk3 = 2.7, logk4 = 2.0 or log β4 = 11.9
The instability constant or the dissociation constant of coordination compounds is defined as the reciprocal of the
formation constant.

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:
The coordination compounds are of great importance. These compounds are widely present in the mineral, plant
and animal worlds and are known to play many important functions in the area of analytical chemistry, metallurgy,
biological systems, industry and medicine. These are described below:

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 Na 2EDTA. 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 in to 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 Mg 2+

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 . it is 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.

MCQ’S ON COORDINATION COMPOUND

1. The property which is not associated with primary valency is

(a) Ionisable (b) Oxidation state (c) Variable (d) Directional

2. The property which is associated with secondary valency is

(a) Ionisable (b) Oxidation state (c) Variable (d) Directional

3. An example of ambidentate ligand is

(a) NH3 (b) CN– (c) H2O (b) Cl–

4. C2O42– and en (ethane – 1,2 – diamine) are examples of _______ligands

(a) Monodentate (b) Bidentate (c) Tridentate (d) Hexadentate

5. The co–ordination number of the central metal ion in [PtCl6]2– (or [Fe(C2O4)3]3– or [Co(en)3]3+ ) is
(a) 2 (b) 4 (c) 6 (d) 3

6. The co–ordination number of the central metal ion in [Ni(NH3)4]+ is

(a) 2 (b) 4 (c) 6 (d) 3

7. The co–ordination sphere in the complex K4[Fe(CN)6] is

(a) K+ (b) Fe2+ (c) CN– (d) [Fe(CN)6]4–

8. The counter ion in the complex K4[Fe(CN)6] is

(a) K+ (b) Fe2+ (c) CN– (d) [Fe(CN)6]4–

9. The co–ordination polyhedron of [Co(NH3)6]3+ is

(a) Tetrahedral (b) Square planar (c) Octahedral (d) Square pyramid

10. The co–ordination polyhedron of [Ni(CO)4] is

(a) Tetrahedral (b) Square planar (c) Octahedral (d) Square pyramid

11. The co–ordination polyhedron of [PtCl4]2– is

(a) Tetrahedral (b) Square planar (c) Octahedral (d) Square pyramid

12. [Pt(NH3)2Cl2] can exhibit

(a) Geometrical isomerism (b) Optical isomerism (c) Ionisation isomerism (d) Linkage isomerism

13. [Co(NH3)4Cl2]+ exhibits

(a) Geometrical isomerism (b) Hydrate isomerism (c) Ionisation isomerism (d) Linkage isomerism

14. [Co(en)2Cl2]+ exhibits

(a) Geometrical isomerism (b) Hydrate isomerism (c) Ionisation isomerism (d) Linkage isomerism

15. [Co(en)3]3+ (or [Pt(en)2Cl2]2– ) exhibits

(a) Optical isomerism (b) Hydrate isomerism (c) Ionisation isomerism (d) Linkage isomerism

16. Only the cis isomer of [Pt(en)2Cl2]2– exhibits

(a) Optical isomerism (b) Hydrate isomerism (c) Ionisation isomerism (d) Linkage isomerism
17. In the complex [Co(NH3)5(NO2)]Cl2 due to the ligand NO2– ion, the complex exhibits
(a) Optical isomerism (b) Hydrate isomerism (c) Ionisation isomerism (d) Linkage isomerism

18. [Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6] exhibit

(a) Co–ordinate isomerism (b) Hydrate isomerism (c) Ionisation isomerism (d) Linkage isomerism

19. [Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4 exhibit

(a) Co–ordinate isomerism (b) Hydrate isomerism (c) Ionisation isomerism (d) Linkage isomerism

20. [Cr(H2O)6]Cl3 (violet) and its solvate isomer [Cr(H2O)5Cl]Cl2.H2O (grey-green) exhibit
(a) Co–ordinate isomerism (b) Hydrate isomerism (c) Ionisation isomerism (d) Linkage isomerism

*********
(b) Hydrate isomerism
(c) Ionisation isomerism
(d) Linkage isomerism