1

9-Coordination Compounds
Coordination Compounds Complex compounds in which transition metal atoms are bound to a number of
anions or neutral molecules (ligands). [Co(NH
3
)
6
]Cl
3


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.
Primary valence is non-directional. Secondary valence are directional. Ligands have different spatial
arrangement depending on coordination no.

Difference between a Double Salt and a Complex
Double salt Complex ion
1. A double salt dissociates completely to give
simpler ions in water.
2. It loses its identity in solution.
Eg: carnallite (KCl.MgCl
2.
6H
2
O), Mohrs salt
[FeSO
4.
(NH
4
)
2
SO
4.
6H
2
O]
1.Complex ions do not dissociate into simpler ions in
water.
2. It retains its identity in solution.
Eg: [Co(NH
3
)
6
]
3+
, [Fe(CN)
6
]4

Definition of Important Terms in Coordination Compounds
Coordination Entity
Constitutes a central metal atom/ ion bonded to a fixed number of ligands [ions or molecules].Eg:[Co(NH
3
)
6
]
3+

Central Atom or Ion
The atom or ion to which a fixed number of ligands are attached in a definite geometrical arrangement around
it in a coordination entity. Eg: Co
3+
in [Co(NH
3
)
6
]
3+
, Fe
3+
in [Fe(CN)
6
]
3

Ligands
Ions or molecules bound to the central metal atom or ion in a coordination entity
Types of ligands
1. Unidentate.
When a ligand is bound to a metal ion through a single donor atom., the ligand is said to be unidentate.
Eg: Cl

, H
2
O or NH
3

2. Didentate
When a ligand is bind to a metal through two donor atoms, the ligand is said to be didentate.
Eg: H
2
NCH
2
CH
2
NH
2
(ethane-1,2-diamine) or C
2
O
4
2
(oxalate)
3. Polydentate.
When a ligand is bound to a metal ion through a several donor atoms., the ligand is said to be polydentate.
Eg: Ethylenediaminetetraacetate ion (EDTA
4
) is
an important hexadentate ligand. It can bind
through two nitrogen and four oxygen atoms to a
central metal ion.

4. Ambidentate ligand
Ligand which can ligate to a metal ion through two different atoms is called ambidentate ligand.
Eg: NO
2

and SCN

ions.
NO
2

ion can coordinate either through nitrogen or through oxygen to a central metal atom/ion.

*Similarly, SCN

ion can coordinate through the sulphur or nitrogen atom.

5. Chelate ligand and chelate complex
When a di- or polydendate ligand uses its 2 or more donor atoms to bind a single metal ion so that a 5 or 6
membered ring are formed, it is said to be a chelate ligand. Such complexes are called chelate complexes.
2

Eg: [Pt Cl
2
(en)]
Dendicity of a ligand
The no.of ligating group present in a ligand. Eg: Dendicity of Cl

, H
2
O or NH
3
is 1,dendicity of oxalate,en is 2
Coordination Number [CN]
Number of ligand-donor atoms bonded directly to the metal.
Eg: The CN of Pt and Ni in [PtCl
6
]
2
and [Ni(NH
3
)
4
]
2+
are 6 and 4 respectively.
Coordination Sphere
The central atom or ion and the ligands attached to it are enclosed in square brackets, which are collectively
known as the coordination sphere.Eg: In K
4
[Fe(CN)
6
], the coordination sphere is [Fe(CN)
6
]
4
, counter ion-K
+
.
Counter ion
The ionisable group present outside the coordination sphere.Eg: In [Co(NH
3
)
6
]Cl
3
, counter ion is Cl
-

Coordination Polyhedron
The spatial arrangement of the ligand atoms which are directly attached to the central atom or ion
o Example: Octahedral, square planar, tetrahedral

Oxidation Number of Central Atom
The charge it would carry if all the ligands are removed along with the electron pairs that are shared with the
central atom. Eg: Oxidation number of copper in [Cu(CN)
4
]
3
is 1, Co in [Co(NH
3
)
6
]
3+
is 3
Homoleptic and Heteroleptic Complexes
Homoleptic Complexes in which the metal is bound to only one kind of ligand [donor group].
Eg: [Co(NH
3
)
6
]
3+

Heteroleptic Complexes in which the metal is bound to more than one kind of ligands [donor groups].
Eg: [Co(NH
3
)
4
Cl
2
]
+

Ligand Charge Normal name IUPAC name
Cl
Br
F
I
CN
OH
NO
3

NO
2

ONO
SCN
NCS
CO
3

SO
4

C
2
O
4

ClO
4

ClO
3

NH
3

H
2
O
CO
en
CH
3
NH
2

CH
3
CH
2
NH
2

NO
PPh
3

-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-2
-2
-2
-1
-1
0
0
0
0
0
0
0
0
Chloride
Bromide
Fluoride
Iodide
Cyanide
Hydroxide
Nitrate
Nitrite
Nitrite
Thiocyanate
Isothiocyanate
Carbonate
Sulphate
oxalate
perchlorate
chlorate
Chlorido
Bromido
Fluorido
Iodo
Cyano/cyanido
Hydroxo/ hydroxido
Nitrato
Nitrito-N
Nitrito-O
Thiocyanato
Isothiocyanato
Carbonato
Sulphato
Oxalato
Perchlorato
chlorato
Ammine
Aqua
Carbonyl
Ethane-1,2-diamine
Methyl amine
Ethyl amine
Nitrosyl
Triphenyl phosphine


3

Naming of Mononuclear Coordination Compounds
The following rules are followed while naming coordination compounds.
The cation is named first in both positively and negatively charged coordination entities.
The ligands are named in alphabetical order before the name of the central atom/ion.
Names of the anionic ligands end in o and those of neutral and cation ligands are the same.
[Exceptions: aqua (H
2
O), ammine (NH
3
), carbonyl (CO), nitrosyl (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. For
example, [NiCl
2
(PPh
3
)
2
] is named as Dichlorobis(triphenylphosphine)nickel(II).
Oxidation state of the metal is indicated by a Roman numeral in parentheses.
If the complex ion is cation, then the metal is named as the element. For example, Fe in a complex
cation is called iron and Pt is called platinum.
If the complex ion is anion, then the metal is named with ate ending. For example, Co in a complex
anion, [Co(SCN)
4
]
2
is called cobaltate.
The neutral complex molecule is named as the complex cation.
Formulas of Mononuclear Coordination Compounds
The following are the rules for writing the formulas.
The central atom is listed first.
The ligands are then listed in the alphabetical order.
Polydentate ligands are also listed in the alphabetical order. In the case of abbreviated ligands, the first
letter of the abbreviation is used for determining the position of the ligands in the alphabetical order.
The formula of the entire coordination entity is enclosed in square brackets. Ligand abbreviations and
formulas for polyatomic ligands are enclosed in parentheses.
There should be no space between the ligands and the metal within a coordination sphere.
For the charged coordination entity, the charge is indicated outside the square brackets, as a right
superscript, with the number before the sign. Example: [Fe(CN)
6
]
3
, [Cr(H
2
O)
6
]
3+
, etc.
The charge of the cation(s) is balanced by the charge of the anion(s).
IUPAC name of some coordination compounds are as follows:
[Ni(CO)
4
] Tetracarbonlynickel(0)
[Co(NH
3
)
3
(H
2
O)
3
]Cl
3
Triamminetriaquachromium(III) chloride
[Pt(NH
3
)
2
Cl(NO
2
)] Diamminechloridonitrito-N-platinum(II)
[CoCl
2
(en)
2
]Cl Dichloridobis(ethane-1,2-diammine)cobalt(III) chloride
K
2
[Zn(OH)
4
] Potassium tetrahydroxozincate(II)
Q) Write the formulas for the following coordination compounds:
(i) Tetraamineaquachloridocobalt(III) chloride (ii) Potassium tetrahydroxozincate(II)
(iii) Potassium trioxalatoaluminate(III (iv) Dichloridobis(ethane-1,2-diamine)cobalt(III)
(v) Tetracarbonylnickel(0)
A) (i) [Co(NH
3
)
4
(H
2
O)Cl]Cl
2
(ii) K
2
[Zn(OH)
4
] (iii) K
3
[Al(C
2
O
4
)
3
(iv) [CoCl
2
(en)
2
]
+
(v) [Ni(CO)
4
]
Q) Write the IUPAC names of the following coordination compounds:
(i) [Pt(NH
3
)
2
Cl(NO
2
)] (ii) K
3
[Cr(C
2
O
4
)
3
] (iii) [CoCl
2
(en)
2
]Cl (iv) [Co(NH
3
)
5
(CO
3
)]Cl (v) Hg[Co(SCN)
4
]
A) (i) Diamminechloridonitrito-N-platinum(II) (ii) Potassium trioxalatochromate(III)
(iii)Dichloridobis(ethane-1,2-diamine)cobalt(III) chloride (iv) Pentaamminecarbonatocobalt(III) chloride
(v) Mercury tetrathiocyanatocobaltate(III)
Q)Write the formulas for the following coordination compounds:
(i) Tetraamminediaquacobalt(III) chloride (ii) Potassium tetracyanonickelate(II) (iii) Tris(ethane1,2
diamine) chromium(III) chloride (iv) Amminebromidochloridonitrito-N-platinate(II) (v)
Dichloridobis(ethane1,2diamine)platinum(IV) nitrate (vi) Iron(III) hexacyanoferrate(II)
A) (i) [Co(NH
3
)
4
(H
2
O)
2
]Cl
3
(ii) K
2
[Ni(CN)
4
] (iii) [Cr(en)
3
]Cl
3
(iv) [Pt(NH
3
)BrCl(NO
2
)]
(v) [PtCl
2
(en)
2
](NO
3
)
2
(vi) Fe
4
[Fe(CN)
6
]
3

Q) Write the IUPAC names of the following coordination compounds:
(i) [Co(NH
3
)
6
]Cl
3
(ii) [Co(NH
3
)
5
Cl]Cl
2
(iii) K
3
[Fe(CN)
6
] (iv) K
3
[Fe(C
2
O
4
)
3
] (v) K
2
[PdCl
4
]
(vi) [Pt(NH
3
)
2
Cl(NH
2
CH
3
)]Cl
(i)Hexaamminecobalt(III) chloride (ii)Pentaamminechoridocobalt(III) chloride
4

(iii)Potassium hexacyanoferrate(III) (iv)Potassium trioxalatoferrate(III) (v)Potassium tetrachloridopalladate(II)
(vi)Diamminechlorido(methylamine)platinum(II) chloride
Q)Using IUPAC norms write the formulas for the following:
(i) Tetrahydroxozincate(II) (vi) Hexaamminecobalt(III) sulphate
(ii) Potassium tetrachloridopalladate(II) (vii) Potassium tri(oxalato)chromate(III)
(iii) Diamminedichloridoplatinum(II) (viii) Hexaammineplatinum(IV)
(iv) Potassium tetracyanonickelate(II) (ix) Tetrabromidocuprate(II)
(v) Pentaamminenitrito-O-cobalt(III) (x) Pentaamminenitrito-N-cobalt(III)
Q)Using IUPAC norms write the systematic names of the following:
(i) [Co(NH
3
)
6
]Cl
3
(iv) [Co(NH
3
)
4
Cl(NO
2
)]Cl (vii) [Ni(NH
3
)
6
]Cl
2

(ii) [Pt(NH
3
)
2
Cl(NH
2
CH
3
)]Cl (v) [Mn(H
2
O)
6
]
2+
(viii) [Co(en)
3
]
3+

(iii) [Ti(H
2
O
)6
]
3+
(vi) [NiCl
4
]
2
(ix) [Ni(CO)
4
]

ISOMERISM

Stereoisomers have same chemical formula and chemical bonds, but have different spatial
arrangement.
Structural isomers have different chemical bonds.
Geometric Isomerism
This type of isomerism arises in heteroleptic complexes due to different possible geometric
arrangements of the ligands.
Generally found with compounds having coordination numbers 4 and 6
Square planar complex of formula [MX
2
L
2
] (X and L are uni-dentate) exhibits geometrical
isomerism cis-isomer and trans-isomer.
Cis isomer - 2 identical ligands are adjacent to each other.
Tras isomer - 2 identical ligands are opposite to each other.
o Example Geometrical isomers of Pt(NH
3
)
2
Cl
2


Octahedral complex of formula [MX
2
L
4
] also exhibits geometrical isomerism.
o Example Geometrical isomers of [Co(NH
3
)
4
)Cl
2
]
+


Octahedral complex of formula [MX
2
(L L)
2
] exhibits geometrical isomerism, where LL is a
bidentate ligand. [e.g., NH
2
CH
2
CH
2
NH
2
(en)]
o Example Geometrical isomers of [CoCl
2
(en)
2
]
5


Octahedral complexes of type [Ma
3
b
3
] exhibit another type of geometrical isomerism facial (fac)
isomer and meridional (mer) isomer.
Example [Co(NH
3
)
3
(NO
2
)
3
]

o Facial (fac) isomer 3 same ligands occupy adjacent
positions at the corners of an octahedral face.
o Meridional (mer) isomer When 3 identical ligands
are around the meridian of the octahedron

1) Why is geometrical isomerism not possible in tetrahedral complexes having two different types of
unidentate ligands coordinated with the central metal ion ?
A)Tetrahedral complexes do not show geometrical isomerism because the relative positions of the
unidentate ligands attached to the central metal atom are the same with respect to each other.

Optical Isomerism
Optical isomers are mirror images that cannot be superimposed on one another. These are called as
enantiomers
The molecules or ions that cannot be superimposed on its mirror image are called chiral.
The two forms are called dextro (d) and laevo (l) depending upon the direction they rotate the plane of
polarised light in a polarimeter.
* Optical isomerism is common in octahedral complexes involving didentate ligands
Example d and l isomer of [Co(en)
3
]
3+


Only cis isomer shows optical activity.
Trans isomer does not show optical isomerism as they form superimposable mirror image(optically
inactive-achiral).


Structural isomerism
Structural isomers the same chemical formula but they have different bonds.
Types of Structural isomerism
6

(i) Linkage isomerism (ii) Coordination isomerism
(iii) Ionisation isomerism (iv) Solvate isomerism
Linkage Isomerism
Linkage isomerism arises in a coordination compound containing ambidentate ligand(which can ligate
through two different atoms)
Eg: [Co(NH
3
)
5
(NO
2
)]Cl
2
and [Co(NH
3
)
5
(ONO)]Cl
2

[Co(H
2
O)
5
(SCN)]Cl
2
and [Co(H
2
O)
5
(NCS)]Cl
2


Coordination Isomerism
This type of isomerism arises from the interchange of ligands between cationic and anionic entities of
different metal ions present in a complex.
Example

Ionisation Isomerism
Compounds which give different ions in solution although they have same composition. (or)
This type of isomerism arises when the counter ion in the complex salt is itself a potential ligand and can
displace a ligand, which can then become the counter ion
o Example

Solvate Isomerism
Compounds with same molecular formula, but differ in no. of solvent molecules inside and outside the
coordination sphere. (or)
Solvate isomers differ by whether or not a solvent molecule is directly bonded to the metal ion or merely
present as free solvent molecules in the crystal lattice.
Example (violet) and (grey green
Known as hydrate isomerism when water is involved as a solvent

Q. Draw structures of geometrical isomers of [Fe(NH
3
)
2
(CN)
4
]

Q. Out of the following two coordination entities which is chiral (optically active)?
(a) cis-[CrCl
2
(ox)
2
]
3
(b) trans-[CrCl
2
(ox)
2
]
3

Out of the two, (a) cis [CrCl
2
(ox)
2
] is chiral (optically active).
Trans is optically inactive, form superimposable mirror image.

Q. Indicate the types of isomerism exhibited and draw the structures for these isomers
(i) K[Cr(H
2
O)
2
(C
2
O
4
)
2
(ii) [Co(en)
3
]Cl
3
(iii) [Co(NH
3
)
5
(NO
2
)](NO
3
)
2
(iv) [Pt(NH
3
)(H
2
O)Cl
2
]
(i) Both geometrical (cis-, trans-) and optical isomers for cis can exist.
(ii) Two optical isomers can exist.
(iii) There are 10 possible isomers. (Hint: There are geometrical, ionisation and linkage isomers possible).
7

(iv) Geometrical (cis-, trans-) isomers can exist.

Q. Give evidence that [Co(NH
3
)
5
Cl]SO
4
and [Co(NH
3
)
5
SO
4
]Cl are ionisation isomers.(or)
Give chemical test to distinguish [Co(NH
3
)
5
Cl]SO
4
and [Co(NH
3
)
5
SO
4
]Cl
Reagent [Co(NH
3
)
5
Cl]SO
4
[Co(NH
3
)
5
SO
4
]Cl
AgNO
3
solution No reaction White ppt of AgCl
BaCl
2
solution White ppt of BaSO
4
No reaction

Valence Bond Theory
The metal atom or ion under the influence of ligands can use its (n1)d, ns, np or ns, np, nd orbitals
for hybridisation, to yield a set of equivalent orbitals of definite geometry such as octahedral,
tetrahedral, square planar, and so on.
These hybridised orbitals are allowed to overlap with ligand orbitals that can donate electron pairs for
bonding.
Coordination number Type of hybridisation Distribution of hybrid
orbitals in space
4
4
5
6
6
sp
3

dsp
2

sp
3
d
sp
3
d
2

d
2
sp
3

Tetrahedral
Square planar
Trigonal bipyramidal
Octahedral
Octahedral
Octahedral Complexes
o The hybridisation involved can be d
2
sp
3
or sp
3
d
2
.
Inner-orbital or low-spin or spin-paired complexes: Complexes that use inner d-orbitals in hybridization.
o Eg: [Co(NH
3
)
6
]
3+
. d
2
sp
3
hybridisation,octahedral, diamagnetic, inner orbital complex.

Outer-orbital or high-spin or spin-free complexes: Complexes that use outer d-orbitals in hybridisation;
Example, [CoF
6
]
3
.sp
3
d
2
hybridisation,octahedral, paramagnetic, outer orbital complex.

Tetrahedral Complexes
o The hybridisation involved is sp
3
, tetrahedral, paramagnetic
o Example: [NiCl
4
]
2

8

o The hybridisation scheme is shown in the following diagram.


Square planar Complexes
o Example: [Ni(CN)
4
]
2
: dsp
2
hybridisation, square planar, paramagnetic.

Magnetic Properties of Coordination Compounds
Complexes with unpaired electron(s) in the orbitals are paramagnetic.
Complexes with no unpaired electron(s) in the orbitals (i.e., all paired electrons) are diamagnetic.

Limitations of Valence Bond Theory
(i) It involves a number of assumptions.
(ii) It does not give quantitative interpretation of magnetic data.
(iii) It does not explain the colour exhibited by coordination compounds.
(iv) It does not give a quantitative interpretation of the thermodynamic or kinetic stabilities of coordination
compounds.
(v) It does not make exact predictions regarding the tetrahedral and square planar structures of 4-coordinate
complexes.
(vi) It does not distinguish between weak and strong ligands.

Crystal-Field Theory
An electrostatic model which considers the metalligand bond to be ionic, which arises from the
electrostatic interaction between the metal ion and the ligand
Ligands are treated as point charges in the case of anions, or dipoles in the case of neutral molecules.
The five d-orbitals in an isolated gaseous metal atom/ion are degenerate (i.e., have the same energy).
Due to the negative fields of the ligands (either anions or the negative ends of dipolar molecules), the
degeneracy of the d-orbitals is lifted, resulting in the splitting of the d-orbitals to give 2 sets of
orbitals- t
2g
and e
g
.

Crystal-Field Splitting in Octahedral Coordination Entities
Crystal-Field Splitting:
Crystal-field splitting is the splitting of the degenerate d orbitals into t
2g
and e
g
due to the presence of ligands.
9

Crystal field splitting energy
o
:
Energy separation between t
2g
and e
g
orbitals
The splitting of d-orbitals in an octahedral crystal-field is shown in the given figure.

The energy separation is denoted by
o
(the subscript o is for octahedral)

Spectrochemical series
The arrangement of ligands in the order of increasing field strength is called spectrochemical series.
Ligands are arranged in a series in the increasing order of the field strength as follows:


Strong field and weak field ligands
Ligands for which
o
(crystal-field splitting) < P (pairing energy), are called weak-field ligands, and
form high-spin complexes. d
4
t
2g
3
e
g
1

Ligands for which
o
(crystal-field splitting) > P (pairing energy), are called strong-field ligands, and
form low-spin complexes. d
4
t
2g
4
e
g
0


Q. How does
o
decides the d orbital configuration?
Weak ligands for which
o
< P form high-spin complexes. d
4
t
2g
3
e
g
1

Strong ligands for which
o
> P, form low-spin complexes. d
4
t
2g
4
e
g
0


Crystal-Field Splitting in Tetrahedral Coordination Entities
The splitting of d-orbitals in a tetrahedral crystal field is shown in the given figure.


t
= (4/9)
o

Colour in Coordination Compounds
The colour of the coordination compounds is attributed to dd transition of electrons.
o For example, the complex [Ti(H
2
O)
6
]
3+
is violet in colour, which is due to dd transition
10


o The energy of yellow-green region is absorbed by the complex, and then, the electron gets
excited from t
2g
level to the e
g
level, i.e.,
In the absence of ligand, crystal field splitting does not occur and hence the substance is colourless. For
example, removal of water from [Ti(H
2
O)
6
]Cl
3
on heating renders it colourless. Similarly, anhydrous CuSO
4

is white, but CuSO
4
.5H
2
O is blue in colour.

Metal Carbonyls
The homoleptic carbonyls (compounds containing
carbonyl ligands only) are formed by most of the
transition metals. Eg Ni(CO)
4
, Fe(CO)
5
, Cr(CO)
6
,
[Mn (CO)
10
], [Co
2
(CO)
8
]

Bonding in metal carbonyls
In metal carbonyls, the metalcarbon bonds have both and characters.
A bond is formed when the carbonyl carbon donates a lone pair of electrons to the vacant d orbital
of the metal.
A bond is formed by the donation of electron pair from the filled metal d- orbital to the vacant anti-
bonding * orbital (also known as back bonding of the carbonyl group).
Thus, a synergic effect is created due to this metal-to-ligand bonding. This synergic effect strengthens
the bond between CO and the metal.

Stability of Coordination Compounds
The stability of a complex in a solution refers to the degree of association between the two
species involved in the state of equilibrium.
Stability can be expressed quantitatively in terms of stability constant or formation constant.

The greater the value of the stability constant, the greater is the stability of the complex.
Free metal ions are usually surrounded by solvent molecules in solution, which will compete with the
ligands molecules (L) and be successively replaced by them as follows:

Where, K
1
, K
2
, = Stepwise stability constants
11

Alternatively, M +4L ML
4

4
= [ML
4
]/[M][L]
4

Where,
1
,
2
, . = Overall stability constant
The stepwise and overall stability constants are therefore related as follows:
or more generally,
The reciprocal of the formation constant is called instability constant or dissociation constant.
Q. Calculate the overall complex dissociation equilibrium constant for the Cu(NH
3
)
4
2+
ion, given that

4
for this complex is 2.1 10
13
.
The overall dissociation constant is the reciprocal of overall stability constant i.e. 1/
4
= 4.7 10
14


Applications of Coordination Compounds
Analytical chemistry
o In many qualitative and quantitative chemical analyses: Colour reactions are given by metal ions
with a number of ligands (especially chelating ligands), which help in detection and estimation.
o Hardness of water can be estimated by simple titration with Na
2
EDTA, which forms stable
complexes with Ca
2+
and Mg
2+
ions.
Metallurgy
o Some important extraction processes of metals such as gold and silver make use of complex
formation. . Gold, for example, combines with cyanide in the presence of oxygen and water to form
the coordination entity [Au(CN)
2
]

in aqueous solution. Gold can be separated in metallic form from

this solution by the addition of zinc .
o Similarly, purification of metals can be achieved through formation and subsequent decomposition of
their coordination compounds. For example, impure nickel is converted to [Ni(CO)
4
], which is
decomposed to yield pure nickel.
Medicinal chemistry
o Chelate therapy is used in medicinal chemistry. For example, EDTA is used in the treatment of lead
poisoning. Cis-platin inhibit the growth of tumours.
o Excess metal ions in plant and animal system can be removed by chelating ligands by forming
complex.
Biological system
o Coordination compounds are of great importance in biological systems. For example, chlorophyll is a
coordination compound of magnesium, haemoglobin is a coordination compound of iron and vitamin
B
12
is a coordination compound of cobalt.

Coordination compounds are used as catalysts. For example, Wilkinson catalyst, [(Ph
3
P)
3
RhCl], is
used for the hydrogenation of alkenes
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.

In black and white photography, the developed film is fixed by washing with hypo solution which
dissolves the undecomposed AgBr to form a complex ion, [Ag(S
2
O
3
)
2
]
3
.
Intext Questions
9.5 Explain on the basis of valence bond theory that [Ni(CN)
4
]
2
ion with square planar structure is diamagnetic
and the [NiCl
4
]
2
ion with tetrahedral geometry is paramagnetic.
9.6 [NiCl
4
]
2
is paramagnetic while [Ni(CO)
4
] is diamagnetic though both are tetrahedral. Why?
9.7 [Fe(H
2
O)
6
]
3+
is strongly paramagnetic whereas [Fe(CN)
6
]
3
is weakly paramagnetic. Explain.
9.8 Explain [Co(NH
3
)
6
]
3+
is an inner orbital complex whereas [Ni(NH
3
)
6
]
2+
is an outer orbital complex.
9.9 Predict the number of unpaired electrons in the square planar [Pt(CN)
4
]
2
ion.
9.10 The hexaquo manganese(II) ion contains five unpaired electrons, while the hexacyanoion contains only one
unpaired electron. Explain using Crystal Field Theory.
Exercises
9.1 Explain the bonding in coordination compounds in terms of Werners postulates.
9.2 FeSO
4
solution mixed with (NH
4
)
2
SO
4
solution in 1:1 molar ratio gives the test of Fe
2+
ion but
CuSO
4
solution mixed with aqueous ammonia in 1:4 molar ratio does not give the test of Cu
2+
ion. Explain y?
12

9.3 Explain with two examples each of the following: coordination entity, ligand, coordination number,
coordination polyhedron, homoleptic and heteroleptic.
9.4 What is meant by unidentate, didentate and ambidentate ligands? Give two examples for each.
9.5 Specify the oxidation numbers of the metals in the following coordination entities:
(i) [Co(H
2
O)(CN)(en)
2
]
2+
(ii) [CoBr
2
(en)
2
]
+
(iii) [PtCl
4
]
2
(iv) K
3
[Fe(CN)
6
] (v) [Cr(NH
3
)
3
Cl
3
]
9.6 Using IUPAC norms write the formulas for the following:
(i) Tetrahydroxozincate(II) (ii) Potassium tetrachloridopalladate(II) (iii) Diamminedichloridoplatinum(II)
(iv) Potassium tetracyanonickelate(II) (v) Pentaamminenitrito-O-cobalt(III)
(vi) Hexaamminecobalt(III) sulphate (vii) Potassium tri(oxalato)chromate(III)
(viii) Hexaammineplatinum(IV)(ix) Tetrabromidocuprate(II) (x) Pentaamminenitrito-N-cobalt(III)
9.7 Using IUPAC norms write the systematic names of the following:
(i) [Co(NH
3
)
6
]Cl
3
(ii) [Pt(NH
3
)2Cl(NH
2
CH
3
)]Cl (iii) [Ti(H
2
O)
6
]
3+
(iv) [Co(NH
3
)
4
Cl(NO
2
)]Cl (v) [Mn(H
2
O)
6
]
2+

(vi)[NiCl
4
]
2
(vii) [Ni(NH
3
)
6
]Cl
2
(viii) [Co(en)
3
]
3+
(ix) [Ni(CO)
4
]
9.8 List various types of isomerism possible for coordination compounds, giving an example of each.
9.9 How many geometrical isomers are possible in the following coordination entities?
(i) [Cr(C
2
O
4
)
3
]
3
(ii) [Co(NH
3
)
3
Cl
3
]
9.10 Draw the structures of optical isomers of:
(i) [Cr(C
2
O
4
)
3
]
3
(ii) [PtCl
2
(en)
2
]
2+
(iii) [Cr(NH
3
)
2
Cl
2
(en)]
+

9.11 Draw all the isomers (geometrical and optical) of:
(i) [CoCl
2
(en)
2
]
+
(ii) [Co(NH
3
)Cl(en)
2
]
2+
(iii) [Co(NH
3
)
2
Cl
2
(en)]
+

9.12 Write geometrical isomers of [Pt(NH
3
)(Br)(Cl)(py)] and how many of these will exhibit optical isomers?
9.13 Aqueous copper sulphate solution (blue in colour) gives: (i) a green precipitate with aqueous potassium
fluoride and(ii) a bright green solution with aqueous potassium chloride. Explain these experimental results.
9.14 What is the coordination entity formed when excess of aq KCN is added to an aq solution ofCuSO
4
? Why
is it that no precipitate of copper sulphide is obtained when H
2
S(g) is passed through this solution?
9.15 Discuss the nature of bonding in the following coordination entities on the basis of valence bond theory:
(i)[Fe(CN)
6
]
4
(ii)[FeF
6
]
3
(iii)[Co(C
2
O
4
)
3
]
3
(iv)[CoF
6
]
3

9.16 Draw figure to show the splitting of d orbitals in an octahedral crystal field.
9.17 What is spectrochemical series? Explain difference between a weak field ligand & a strong field ligand.
9.18 What is crystal field splitting energy? How does the magnitude of
o
decide the actual configuration of d
orbitals in a coordination entity?
9.19 [Cr(NH
3
)
6
]
3+
is paramagnetic while [Ni(CN)
4
]
2
is diamagnetic. Explain why?
9.20 A solution of [Ni(H
2
O)
6
]
2+
is green but a solution of [Ni(CN)
4
]
2
is colorless. Explain.
9.21 [Fe(CN)
6
]
4
and [Fe(H
2
O]
2+
are of different colours in dilute solutions. why?
9.22 Discuss the nature of bonding in metal carbonyls.
9.23 Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the
following complexes: (i) K
3
[Co(C
2
O
4
)
3
] (ii)cis-[Cr(en)
2
Cl
2
]Cl (iii)(NH
4
)
2
[CoF
4
] (iv) [Mn(H
2
O)
6
]SO
4

9.24 Write down the IUPAC name for each of the following complexes and indicate the oxidation state,
electronic configuration and coordination number. Alsogive stereochemistry and magnetic moment of the
complex:(i) K[Cr(H
2
O)
2
(C
2
O
4
)
2
].3H
2
O (ii) [Co(NH
3
)
5
Cl-]Cl
2
(iii) CrCl
3
(py)
3
(iv) Cs[FeCl
4
] (v) K
4
[Mn(CN)
6
]
9.25 What is meant by stability of a coordination compound in solution? State the factors which govern
stability of complexes.
9.26 What is meant by the chelate effect? Give an example.
9.27 Discuss briefly giving an example in each case the role of coordination compounds in:
(i) biological systems (ii) medicinal chemistry (iii) analytical chemistry (iv) extraction/metallurgy of metals.
9.28 How many ions are produced from the complex [Co(NH
3
)
6
]Cl
2
in solution?(i) 6 (ii) 4 (iii) 3 (iv) 2
9.29 Amongst the following ions which one has the highest magnetic moment value?
(i) [Cr(H
2
O)
6
]
3+
(ii) [Fe(H
2
O)
6
]
2+
(iii) [Zn(H
2
O)
6
]
2+

9.30 The oxidation number of cobalt in K[Co(CO)
4
] is (i) +1 (ii) +3 (iii) 1 (iv) 3
9.31 Amongst the following, the most stable complex is
(i) [Fe(H
2
O)
6
]
3+
(ii) [Fe(NH
3
)
6
]
3+
(iii) [Fe(C
2
O
4
)
3
]
3
(iv) [FeCl
6
]
3

9.32 What will be the correct order for the wavelengths of absorption in the visible region for the following:
[Ni(NO
2
)
6
]
4
, [Ni(NH
3
)
6
]
2+
, [Ni(H
2
O)
6
]
2+
?