9.

Coordination Compounds
Coordination compounds are complex compounds in which transition metal atoms are
bound to a number of anions or neutral molecules.
.

Coordination entity: A coordination entity constitutes a central metal

atom or ion bonded to a fixed number of ions or molecules. Example:
in K4[Fe(CN)6], [Fe(CN)6]4- represents coordination entity.
Counter ions: The ions present outside the coordination sphere are
called counter ions. For example: in the complex K4[Fe(CN)6], K+ is the
counter ion.

Postulates of Werners theory of coordination compounds:

In coordination compounds, there are two types of linkages (valences) primary
and secondary.
The primary valences are ionisable and are satisfied by negative ions.
The secondary valences are non-ionisable and are satisfied by negative ions or
neutral molecules. The secondary valence is equal to the coordination number of a
metal and remains fixed for a metal.
Different coordination numbers have characteristic spatial arrangement of the ions
or groups bound by the secondary linkages.
Difference between a double salt and a complex:
In water, a double salt dissociates completely to give simpler ions. Examples of
double salt: carnallite (KCl. MgCl2. 6H2O), Mohrs salt [FeSO4. (NH4)2 SO4. 6H2O]
Complex ions do not dissociate further to give simpler ions. For example,
[Fe(CN)6]4, [Fe(C2O4)3]3
Ligands:
Ions or molecules bound to the central metal atom or ion in the coordination entity
.

Denticity: The number ofdonor

atoms present in ligand

Didentate
H 2 N CH 2 CH 2

NH 2

Ethane 1, 2 diamine

C 2 O 42
Oxalate

Polydentate

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DPS JODHPUR

Ambidentate
(Can bind through two different atoms)

Coordination number: Number of ligand donor atoms bonded directly to the metal
Coordination polyhedral:

Homoleptic and heteroleptic complexes:

Homoleptic complexes: In which metal is bound to only one kind of donor groups,
e.g., [Co(NH3)6]3+
Heteroleptic complexes: In which metal is bound to more than one kind of donor
groups, e.g., [Co(NH3)4Cl2]+
Naming of mononuclear coordination compounds:
The cation is named first in both physically and negatively charged coordination
entities.

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DPS JODHPUR

The ligands are named in alphabetical order, before the name of the central
atom/ion.
Names of the anionic ligands end in o.
[Exceptions: aqua (H2O), ammine (NH3), carbonyl (CO), nitroryl (NO)]
To indicate the number of the individual ligands, the prefixes mono, di, tri,
etc., are used. If these prefixes are present in the names of ligands, then the terms
bis, tris, tetrakis, etc., are used.
Oxidation state of the metal is indicated in Roman numerals, in parentheses.
If the complex ion is cation, then the metal is named as the element.
If the complex ion is anion, then the metal is named with ate ending.
The neutral complex molecule is named as the complex cation.

1. [Cr(NH3)3(H2O)3]Cl3 is named as:

triamminetriaquachromium(III) chloride
2. [Co(H2NCH2CH2NH2)3]2(SO4)3 is named as:
tris(ethane-1,2diammine)cobalt(III) sulphate
3. [Ag(NH3)2][Ag(CN)2] is named as:
diamminesilver(I) dicyanoargentate(I)
4. K2[Zn(OH)4]
Potassium tetrahydroxozincate(II)
5. [Co(NH3)4(H2O)Cl]Cl2
Tetraammineaquachloridocobalt(III) chloride

6.Hg[Co(SCN)4]
.Mercury tetrathiocyanatocobaltate(III)
7. [Pt(NH3)2Cl(NO2)]
. Diamminechloridonitrito-N-platinum(II)
8.K3[Cr(C2O4)3]
Potassium trioxalatochromate(III)

Using IUPAC norms write the formulas for the following:

(i)Potassiumtetracyanonickelate(II)

(ii) Pentaamminenitrito-O-cobalt(III)
(iii) Hexaamminecobalt(III) sulphate
(iv) K2[Ni(CN)4]

(v) [Co(ONO) (NH3)5]2+

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(vi) [Co(NH3)6]2 (SO4)3

DPS JODHPUR

Isomerism in coordination compounds:

Complexes of co-ordination number 6

Geometric isomers ,Cis and trans positions

Two Cis positions:- position at0 90 angle

0 angle
Two trans positions:- position at 180

In Tetrahedral geometry : In this case all the four ligands are

symmetrically arranged with respect to one another as such geometrical
isomerism is not possible.
Geometry of molecule having
Co-ordination No. 4

Tetrahedral
(Will not show G.I.)

Stereoisomerism

Square Planar

Bidentate Ligand

Mondentate Ligand

Geometrical isomerism:

"

MA BC
(Will
show G.I.)

MA
(Will not show G.I.)

MA!B

(Will not
show G.I.)

MA B

(Will
show G.I.)

MAB!

MABCD
(Will
show G.I.)

Symmetrical
bidentate ligand

Unsymmetrical
bidentate ligand

M(AA)

M(AA)

(Will not
show G.I.)

(Will
show G.I.)

(Will not
show G.I.)

Optical isomerism:
Optical isomers (enantiomers) are mirror images which cannot be superimposed
on one another.
The molecules or ions which cannot be superimposed are called chiral.

MUKESH SHARMA

DPS JODHPUR
Slide 21 of 55

in [PtCl2(en) 2] ,

optical isomerism in complex with three bidentate ligand

only cis form is optical active

Structural isomerism
Linkage isomerism:
Arises due to the presence of ambidentate ligand

Coordination isomerism:
Arises due to the interchange of ligands between cationic and anionic entities
of different metal ions
Co NH3

Cr CN

and Cr NH3

Co CN

Ionisation isomerism:
Arises due to the interchange of ligands between the inside and the outside
of the coordination sphere
Co NH3 5 SO 4 Br and Co NH3 5 Br SO4

Solvate isomerism (Hydrate isomerism when solvent is water):

Arises depending upon whether a solvent molecule is directly bonded to the
metal ion or is present as a free solvent molecule.
Cr H 2O6

Cl3 and Cr H 2O 5 Cl Cl 2 H 2O

violet

(grey green)

Valence bond theory:

Coordination
number
4

Type of
hybridisation
sp3

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Distribution of hybrid
orbitals in space
Tetrahedral

DPS JODHPUR

dsp2
sp3d
sp3d2
d2sp3

4
5
6
6

Square planar
Trigonal bipyramidal
Octahedral
Octahedral

Inner-orbital or low spin or spin-paired complexes: Complexes that use inner d

orbitals in hybridisation, e.g., [Co(NH3)6]3+
Outer-orbital or high spin or spin-free complexes: Complexes that use outer d
orbitals in hybridisation, e.g., [CoF6]3
Limitations of valence bond theory:
A number of assumptions are involved.
Quantitative interpretation of magnetic data is not given.
The exhibition of colour by coordination compounds is not explained.
The thermodynamic or kinetic stabilities of coordination compounds are not
quantitatively interpreted.
Whether a complex of coordination number 4 is tetrahedral or square planar cannot
be exactly predicted.
Weak and strong ligands cannot be distinguished.
Magnetic

illustration of Effect of ligand on Ni2+ ion in co No=4

ure

in both complex Ni is same with +2 state in but in ist Clis weak ligand and can not force pairing of e so
3d orbital can be made vacant so it use 4s, 4p to have
SP3 hybrid but in 2nd case CN- do frced pairing and creat vacant
d orbital in 3d subshell and can hve dsp2 hybridisation

[Ni(Cl)4]2-

[Ni(CN)4]2-

illustration of Effect of ligand on Fe3+ ion in co No=6

The electronic configuration of the free Fe3+ ion is:

The electronic configuration of the free Fe ion

Requirement of vaccant orbital =6,[SP3d2 or d2SP3]
two d, one s, three p
Vacant orbital available in 3d =zero

Requirement of vaccant orbital =6,[SP3d2 or d2SP3]

two d, one s, three p Vacant orbital available in 3d =zero
CN- force e- in 3d to give two d orbital vacant

MUKESH SHARMA

DPS JODHPUR

Crystal-field theory:
[Crystal-field splitting is the splitting of the degenerate energy levels due to the presence of
ligands.]
Crystal-field splitting in octahedral coordination entities:

Spectrochemical series:
I

Br
H2O

SCN
NCS

Cl

S2

EDTA 4

OH

NH3

en

C2O24
CN

CO

Ligands for which 0 (crystal-field splitting) < P (pairing energy) are called
weak-field ligands, and form high-spin complexes.
Ligands for which o (crystal-field splitting) > P (pairing energy), are
called strong-field ligands, and form low-spin complexes.

Crystal-field splitting in tetrahedral coordination entities:

t = (4/9) 0

Colour in coordination compounds:

The colour of the coordination compounds is attributed to dd transition of electrons.
Limitations of the crystal-field theory:
Anionic ligands are assumed to exert the greatest splitting effect. But the anionic
ligands are found at the lower end of the spectrochemical series.
Crystal-field theory does not take into account the covalent character of bonding
between ligand and the central metal atom.

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DPS JODHPUR

Electron Configuration in d-Orbitals as per

Electron Configuration in d-Orbitals as per

nature of ligand

CFSE and paring energy

d4

Hunds rule

pairing energy considerations

> P

< P

low spin d4

high spin d4

Pairing is easy

Pairing is difficult

in case of strong ligand CFSE > PE i.e pairing is done before filling in
higer set of orbital ligand like ammonia, cynied , en, ox etc are strong
ligand

d in Weak and Strong Field Ligands

6

Number of unpaired electron = 4

[ Fe(CN) ]
6

Fe = 3d
Since CN is strong field ligand all the electrons get paired.

No unpaired electrons so diamegnetic

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DPS JODHPUR

Metal carbonyl and their synergic bonding

(1)

Metal carbonyl show exceptionally high stability than the expected stability by their normal bonding
This can be explained by concept of back bonding.

(2)

Metal have 2 types of orbital

(3)

(a)

Vacant valence orbitals

(b)

Some partilly d-orbitals.

In metal carbonyls metals forms a

bond with ligand where ligand donates its e pair into vacant

orbitals of metals.
(4)

The excess e deposited on metal by the ligand is relieved by back bonding where metal donates
back from its filled orbitals into vacant anti-bonding orbitals of CO. This extra back-bonding is called

Synergic back-bonding which imparts extra bond strength and metal carbonyls turns more stable

CO

OC
Ni

CO
Fe

OC

CO

OC

CO
CO

CO
Fe(CO)5
Trigonal bipyramidal

Ni(CO)4
Tetrahedral

stability of complexes and stability constant

(a)

The values of stability constants differ widely depending on the nature of the metal ion and
the ligand. In general, higher the charge density on the central ion, the greater is the stability
of its complexes, i.e., the higher value of

charge g
-------------, the greater is the stability of its
radius of the ion

complexes.
()

Chelating

ligands form more stable complexes as compared to monodentate ligands.

(c)

The more basic a ligand, the greater is the ease with which it can donate its lone pairs of
electrons and therefore, the greater is the stability of the complexes formed by it.

(d)

The higher the oxidtation state of the metal, the more stable is the complex. The charge
density of Co3+ ion is more than Co2+ ion and thus, [Co(NH3)6]3+ is more stable than
[Co(NH3)6]2+. Similarly, [Fe(CN)6]3 is more stable than [Fe(CN)6]4.

(e)

The cyano and ammine complexes are far more stable than those formed by halide ions. This
is due to the fact that NH3 and CN are strong Lewis bases.

(f)

The complexes of bivalent cations (M2+) of 3d-series show the following order of stability :
Cation

Mn2+

Fe2+

Co2+

Ni2+

Cu2+

Ionic size

0.91

0.83

0.82

0.78

0.69

Stability of the complex

decrease
increase

MUKESH SHARMA

DPS JODHPUR