COORDINATION

COMPOUNDS
Werner’s theory
•A coordination compound shows two type of linkages.
•Primary valancies are ionisable and are satisfied by
negative ions.
[COCl2(NH3)4] Cl [COCl(NH3)5] Cl2

•Secondary valancies are non ionisable and are

satisfied by negative ions or neutral molecules.
[COCl2(NH3)4] Cl [COCl(NH3)5] Cl2

•The secondary valancies have different spatial

arrangements which determines its geometry.
 EXAMPLE 9.1
On the basis of the following observations made with
aqueous solutions, assign secondary valences to
metals in the following compounds:
Simple salt:
*Simple salts ionise when dissolved in
water. Formed by the neutralization of acid
and alkali.(eg) NaCl.

Molecular or addition compounds:

Two or more simple salt solutions are mixed in
stoichiometric proportions and allowed to
evaporate to give crystals of new compounds called
molecular or addition compounds separate out.
 Molecular or Addition compounds are of two categories
(i)Double salts:
Exist only in crystal lattices but break down into their constituent ions
when dissolved in water or any other solvent.
(eg) Carnallite :KCl.MgCl2.6H2O
Mohr’s salt : FeSO4.(NH4)2SO4. 6H2O
Potash alum :K2SO4Al2(SO4)3.24H2O
(ii)Coordination compounds(or)
Complex compounds:
They retain their identities even when dissolved in water
or any other solvent and their properties are completely
different from those of the constituents.
(eg)Potassium ferrocyanide is a complex compound. It is
formed by adding KCN to a saturated solution of ferrous
cyanide.
Fe(CN)2 + 4KCN → K4[Fe(CN)6]
When K4[Fe(CN)6] is dissolved in water, it does not give
the usual tests for Fe2+ and CN– ions indicating that these
ions which were originally present are not formed.
Actually these ions are present in the form of
a new ion called ferrocyanide ion which is a
complex ion and does not ionise into
constituent ions.
K4[Fe(CN)6] → 4K+ + [Fe(CN)6]4—
The dissociation of ferrocyanide ion is so negligible,
as not to confirm to the usual tests of the ferrous ion.
TERMS USED IN COORDINATION COMPOUNDS:
1.Central ion or Centre of coordination:
The cation to which one or more neutral molecules
or anions are attached is called the centre of
coordination.
Central ion acts as an acceptor and thus it has to accommodate
electron pairs donated by the donor atom (ligand) ,it must have
empty d orbitals.

(eg)[Ni(NH3)6]2+ [Fe(CN)6]3—

Ni2+ and Fe3+ are the central ions.

 LIGAND:
• Any atom ,ion or neutral molecule which is capable of donating a pair of
electrons to the central atom in the coordination sphere is called ligand.
• In a ligand the particular atom which actually donates the electron pair is called the
donor atom.
• The ligand containing one, two or more donor atoms are known as
unidentate,bidentate and polydentate respectively.
• When polydentate ligands uses its donor atoms to bind a single metal ion it is said
to be a chelate ligand.
• The number of such ligating groups is called the denticity of the ligand.
 Ligand which can ligate through two different atoms
is called ambidentate ligand. Examples of such
ligands are the NO2– and SCN– ions. NO2– 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.
Formulas and Name of Some Common
Formula Name Ligands
H2O aqua
NH3 ammine
CO carbonyl
NO nitrosyl
H2NC2H4NH2 ethylenediamine
OH- hydroxo
O2- oxo
F- fluorido
Cl- chlorido
Br- bromido
I- iodo
CN- cyano
-NCS- isothiocyanato*
-SCN- thiocyanato*
SO42- sulfato
SO32- sulfito
NO3- nitrato*
-NO2- nitro*
-ONO- nitrito*
CO32- carbonato
3.COORDINATION NUMBER:
The total number of ligands attached to the central
ion is known as the coordination number of that ion.
(eg) [Ag(NH3)2]+ and [Cu(H2O)4]2+
the coordination numbers of Ag and Cu are 2 and 4
respectively.
4.COORDINATION SPHERE :
The central metal atom and the ligands directly
attached to it enclosed in square bracket are
collectively termed as the coordination sphere.
Coordination sphere is written inside square bracket
(eg) [Co(NH3)6]3+
Coordination polyhedron
The spatial arrangement of the ligands which is directly
attached to the central atom .
Homoleptic complexes
Complexes in which the central atom is bound to one
kind of ligands.
[Ni(NH3)6]2+
Heteroleptic complexes.
Complexes in which the central atom is bound to more
than one kind of ligands.
[COCl(NH3)5] Cl2
5.OXIDATION NUMBER:
Oxidation number of the central atom is the electric charge
it would carry if all the ligands are removed with the
electron pairs that are shared with the central atom.
Fe in [Fe (CN)6]4-- is +2
Co in [Co(NH3)6]3+ is +3
Ni in Ni(CO)4 is zero
DETERMINATION OF OXIDATION NUMBER AND
COORDINATION NUMBER OF A METAL ATOM OR ION IN A
COMPLEX:
K4[Fe(CN)6] Coordination number is 6 (6 CN-- ions)
The complex carries 4 –ve charges
[Fe(CN)6]4– x + (-6) = -4 x = 2
Iron is present as Fe2+
 Nomenclature of Coordination Compounds
1.The cation or positive part of the complex is named
first followed by the anion (negative part).
(eg) K4[Fe(CN)6] Potassiumhexacyanoferrate (II)
2.While naming the coordination sphere ,ligands are
named first and the central atom last.
3.The following rules pertain to the names of ligands.
a.The ligands are named first and the central atom last.
b. Ligands are named in alphabetical order
irrespective of their charges.
c. Neutral ligands are named the same as the
molecule, except for a few such as H2O (aqua)and
NH3 (ammine), which have special names.
d. Anionic ligands are named by adding –o to the stem
of the usual name, such as chloro for Cl- and sulfato
for SO42-.
4. Prefix di, tri etc is used if more than one of that
ligand is bonded to the central atom. For
example, the ligands in PtCl42- are named
tetrachloro, and the ligands in Co(NH3)4Cl2+ are
named tetraamminedichloro.

5. If the name of the ligand include numerical prefix

(ethylenediamine) then prefixes such as (bis-
tris-, tetrakis-, pentakis-, hexakis-, etc.).
For example, the ligands in Co(en)33+ are
named trisethylenediamine.
6.For a cationic complex ion or a nonionic
compound, the central atom is given its ordinary
name followed by its oxidation number in Roman
numerals, enclosed in parentheses.
(eg) [Cr(H2O)5Cl]2+ is named
pentaaquachlorochromium(III) ion, and

[Cr(NH3)3Cl3] is named as
triamminetrichlorochromium(III).

7. For anionic complex ions, the suffix –ate is added

to the name of the central atom, followed by the
oxidation number in Roman numerals, enclosed in
parentheses.
(eg) [Cr(CN)6]3- is named as
hexacyanochromate (III) ion.
 Writing the formula of complexes:

[Cr(H2O)3Cl(en)]2+ [Cr(H2O)3Cl(en)]SO4

1.The complex ion should be enclosed by square brackets .

2.The metal is (written ) first ,then the ligands in alphabetical
order
The first letter of the abbreviation is used to determine the
position in alphabetical order.
Ligand abbreviations and when the ligands are polyatomic it is
enclosed in parentheses.
The formula of the coordination entity is enclosed in square
brackets.
The charge of the coordination entity is written as right
superscript with number before the sign when written without
counter ions.
The charge of the cation is balanced by the anion.
Cation is written first followed by anion.
 Nomenclature: IUPAC Rules
Transition Name if in Cationic Name if in Anionic Complex
Metal Complex
Sc Scandium Scandate
Ti titanium titanate
V vanadium vanadate
Cr chromium chromate
Mn manganese manganate
Fe iron ferrate
Co cobalt cobaltate
Ni nickel nickelate
Cu Copper cuprate
Zn Zinc zincate
Give the name of the following coordination
compounds.
1. [CoBr(NH3)5]SO4
2. [Fe(NH3)6][Cr(CN)6]
3.[Co(SO4)(NH3)5]+
4. [Fe(OH)(H2O)5]2+
Give the molecular formulas of the following
coordination compounds.
1. hexaammineiron(III) nitrate
2. ammonium tetrachlorocuprate(II)
3. sodium monochloropentacyanoferrate(III)
4. potassium hexafluorocobaltate(III)
 Answers
1.pentaamminebromocobalt(III) sulfate
2. hexaammineiron(III) hexacyanochromate (III)
3. pentaamminesulfatocobalt(III) ion
4. pentaaquahydroxoiron(III) ion

1.Fe[(NH3)6](NO3)3
2. (NH4)2[CuCl4]
3. Na3[FeCl(CN)5]
4. K3[CoF6]
20_441

Isomers
(same formula but different properties)

Structural Stereoisomers
isomers (same bonds, different
(different bonds) spatial arrangements)

Geometric
Coordination Linkage Optical
(cis-trans)
isomerism isomerism isomerism
isomerism
 Linkage Isomerism
Linkage isomerism arises in a coordination
compound containing ambidentate ligand. A
simple example is provided by complexes
containing the thiocyanate ligand, NCS–,
which may bind through the nitrogen to give
M–NCS or through sulphur to give M–SCN.
Jørgensen discovered such behaviour in the
complex [Co(NH3)5(NO2)]Cl2, which is
obtained as the red form, in which the nitrite
ligand is bound through oxygen (–ONO), and
as the yellow form, in which the nitrite ligand
is bound through nitrogen (–NO2).
 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. An example is provided by
[Co(NH3)6][Cr(CN)6], in which the NH3
ligands are bound to Co3+ and the CN–
ligands to Cr3+. In its coordination isomer
[Cr(NH3)6][Co(CN)6], the NH3 ligands are
bound to Cr3+ and the CN– ligands to Co3+.
 Ionisation Isomerism
This form of isomerism arises when the
counter ion in a complex salt is itself a
potential ligand and can displace a
ligand which can then become the
counter ion. An example is provided by
the ionisation isomers
[Co(NH3)5SO4]Br and
[Co(NH3)5Br]SO4.
 Solvate Isomerism
This form of isomerism is known as ‘hydrate
isomerism’ in case where water is involved as
a solvent. This is similar to ionisation
isomerism. 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. An
example is provided by the aqua complex
[Cr(H2O)6]Cl3 (violet) and its solvate isomer
[Cr(H2O)5Cl]Cl2.H2O (grey-green).
 Structural Isomerism 1
Coordination isomerism:
Composition of the complex ion varies.

[Cr(NH3)5SO4]Br
and [Cr(NH3)5Br]SO4
 Structural Isomerism 2
Ligand isomerism:
Same complex ion structure but point
of attachment of at least one of the ligands
differs.

[Co(NH3)4(NO2)Cl]Cl
and [Co(NH3)4(ONO)Cl]Cl
 Linkage Isomers

[Co(NH3)5(NO2)]Cl2 [Co(NH3)5(ONO)]Cl2
Pentaamminenitrocobalt(III) Pentaamminenitritocobalt
chloride (III)
 Stereoisomerism 1
Geometric isomerism (cis-trans):

Atoms or groups arranged

differently spatially relative to metal ion

Pt(NH3)2Cl2
 STEREOISOMERISM
Stereoisomers have the same chemical
formula and chemical bonds but they
have different spatial arrangement.
 Geometric Isomerism
This type of isomerism arises in
heteroleptic complexes due to different
possible geometric arrangements of
the ligands. Important examples of this
behaviour are found with coordination
numbers 4 and 6.
 In a square planar complex of formula
[MX2L2] (X and L are unidentate), the two
ligands X may be arranged adjacent to each
other in a cis isomer, or opposite to each other
in a trans isomer
Similar behaviour is possible in octahedral
complexes of formula [MX2L4] in which the
two ligands X may be oriented cis or trans to
each other
 CN =4
MA2X2
MA2XY
MABXY

A, B = Neutral ligands
X, Y = Anionic ligands
 CN = 6
MA4X2
MA4XY
M(L-L)2X2

MA3X3
20_444
Cl
Cl
H3N NH3
H3N NH3
Co Co

H3N NH3 H3N Cl

Cl NH3

Cl Cl

Co Co
Cl

Cl
(a) (b)
This type of isomerism also arises when didentate
ligands L–L [e.g., NH2 CH2 CH2 NH2 (en)] are
present in complexes of formula [MX2(L–L)2]
Another type of geometrical isomerism occurs
in octahedral coordination entities of the type
[Ma3b3] like [Co(NH3)3(NO2)3].
If three donor atoms of the same ligands occupy
adjacent positions at the corners of an
octahedral face, we have the facial (fac) isomer.
When the positions are around the meridian of
the octahedron, we get the meridional (mer)
isomer
 OPTICAL ISOMERISM
This type of isomerism is exhibited by
molecules which do not have a plane of
symmetry.
These isomers are mirror images that
cannot be superimposed on one
another. These are called as
enantiomers.
• The molecules or ions that cannot be
superimposed 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 (d
rotates to the right, l to the left).
 Optical isomerism:
Stereoisomerism 2
Have opposite effects on plane-
20_446
polarized light
(no superimposable mirror images)
Polarizing
filter

Tube
containing
Unpolarized
sample
light 
Polarized
light

Rotated
polarized light
20_448

Mirror image
of right hand
Left hand
Right hand
In a coordination entity of the type
[PtCl2(en)2]2+, only the cis-isomer shows
optical activity
20_449

N N
Mirror image
Co
N N of Isomer I

N
N N

N N N N
Co Co
N N N N
Isomer I Isomer II
N N
20_450

Cl The trans isomer and Cl Isomer II cannot be

its mirror image are superimposed exactly
N N identical. They are not N N on isomer I. They are
Co isomers of each other. Co not identical structures.
N N N Cl
Cl Cl Cl
Cl N
N N N Cl N N
trans Co cis Co Co
N N N N N Cl

Cl Isomer I N Isomer II N

Isomer II has the same

structure as the mirror
(a) (b) image of isomer I.
 Valence Bond Theory
According to this theory, the metal atom or ion under the
influence of ligands can use its (n-1)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.
It is usually possible to predict the geometry of a
complex from the knowledge of its magnetic
behaviour on the basis of the valence bond theory.

In the diamagnetic octahedral complex,

[Co(NH3)6]3+ , the cobalt ion is in +3 oxidation state
and has the electronic configuration 3d6. The
hybridisation scheme is as shown
 Thus, the complex has octahedral
geometry and is diamagnetic because of
the absence of unpaired electron.

In the formation of this complex, since

the inner d orbital (3d) is used in
hybridisation, the complex,
[Co(NH3)6]3+ is called an inner orbital
or low spin or spin paired complex.
 The paramagnetic octahedral complex, [CoF6]3–
uses outer orbital (4d ) in hybridisation (sp3d2). It
is thus called outer orbital or high spin or spin
free complex.
In tetrahedral complexes one s and three p orbitals
are hybridised to form four equivalent orbitals
oriented tetrahedrally. Example [NiCl4]2-.
Similarly, [Ni(CO)4] has tetrahedral geometry but is
diamagnetic
 INTEXT 9.5
Explain on the basis of valence bond
theory that [Ni(CN)4]2– ion with square
planar structure is diamagnetic and the
[NiCl4]2– ion with tetrahedral geometry
is paramagnetic
 Magnetic Properties of
Coordination Compounds
A critical study of the magnetic data of coordination compounds
of metals of the first transition series reveals some
complications. For metal ions with upto three electrons in the d
orbitals, like Ti3+ (d1); V3+ (d2); Cr3+ (d3); two vacant d
orbitals are available for octahedral hybridisation with 4s and 4p
orbitals. The magnetic behaviour of these free ions and their
coordination entities is similar. When more than three 3d
electrons are present, the required pair of 3d orbitals for
octahedral hybridisation is not directly available (as a
consequence of Hund’s rule). Thus, for d4 (Cr2+, Mn3+), d5
(Mn2+, Fe3+), d6 (Fe2+, Co3+) cases, a vacant pair of d
orbitals results only by pairing of 3d electrons which leaves two,
one and zero unpaired electrons, respectively
 EXAMPLE 9.7
The spin only magnetic moment of
[MnBr4]2– is 5.9 BM. Predict the
geometry of the complex ion ?
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
Focus: energies of the d orbitals

Assumptions
1. Ligands: negative
point charges
2. Metal-ligand bonding: entirely ionic

strong-field (low-spin): large splitting of d

orbitals
weak-field (high-spin): small splitting of d
orbitals
 Postulates
It considers the metal-ligand bond to be
ionic arising purely from electrostatic
interactions between the metal ion and
the ligand.
Ligands are treated as point charges in
case of anions or dipoles in case of
neutral molecules.
The five d orbitals in an isolated
gaseous metal atom/ion have same
energy, i.e., they are degenerate.
This degeneracy is maintained if a
spherically symmetrical field of negative
charges surrounds the metal atom/ion.
However, when this negative field is
due to ligands in a complex, it becomes
asymmetrical and the degeneracy of the
d orbitals is lifted. It results in splitting of
the d orbitals
20_454

eg(d z2, d x 2 – y2)


t2g (d xz, d yz, d xy)

 = crystal field splitting

Free metal ion

3d orbital
energies
 CRYSTAL FIELD
STABILIZATION ENERGY CFSE
The amount of stabilization provided by
splitting of the d-orbitals into two levels
is known as Crystal Field Stabilization
energy.
The crystal field splitting, Δo, depends
upon the field produced by the ligand and
charge on the metal ion. Some ligands are
able to produce strong fields in which
case, the splitting will be large whereas
others produce weak fields and
consequently result in small splitting of d
orbitals.
SPECTROCHEMICAL SERIES

Ligands can be arranged in a series in

the order of increasing field strength as
given below:
I– < Br– < SCN– < Cl– < S2– < F – < OH–
< C2O42– < H2O < NCS– < edta4– < NH3 <
en < CN– < CO
Such a series is termed as
spectrochemical series.
High spin Low spin
20_459

Tetrahedral Complexes

– dz 2 dx2 – y2
– –
– –– –
– –
–

dxy dxz dyz

(a) (b)
 Crystal field splitting in
tetrahedral coordination entities
In tetrahedral coordination entity formation,
the d orbital splitting is inverted and is
smaller as compared to the octahedral field
splitting. For the same metal, the same
ligands and metal-ligand distances, it can be
shown that Δt = (4/9) Δ0. Consequently, the
orbital splitting energies are not sufficiently
large for forcing pairing and, therefore, low
spin configurations are rarely observed.
Colour in Coordination
Compounds
[Ti(H2O)6]3+, is violet in colour. This is an
octahedral complex where the single electron
(Ti3+ is a 3d1 system) in the metal d orbital is in
the t2g level in the ground state of the complex.
The next higher state available for the electron is
the empty eg level. If light corresponding to the
energy of yellow-green region is absorbed by the
complex, it would excite the electron from t2g
level to the eg level (t2g1eg0 → t2g0eg1).
Consequently, the complex appears violet in
colour
[V(H2O)6]2+ [V(H2O)6]3+

[Cr(NH3)6]3+ [Cr(NH3)5Cl]2+s
 It is important to note that in the absence
of ligand, crystal field splitting does not
occur and hence the substance is
colourless. For example, removal of
water from [Ti(H2O)6]Cl3 on heating
renders it colourless. Similarly,
anhydrous CuSO4 is white, but
CuSO4.5H2O is blue in colour.
 The influence of the ligand on the colour of a
complex may be illustrated by considering
the [Ni(H2O)6]2+ complex, which forms
when nickel(II) chloride is dissolved in water.
If the didentate ligand, ethane-1,2-
diamine(en) is progressively added in the
molar ratios en:Ni, 1:1, 2:1, 3:1, the
following series of reactions and their
associated colour changes occur:
20_461

Square Planar & Linear Complexes

dx2 - y2
dz2

E
E dxy dxz dyz
dz2
dxy dx2 - y2
dxz dyz
Free metal ion Complex
Free metal ion Complex

M
M z
y
(a) (b)

Approach along x-and y-axes Approach along z-axis

Hemoglobin & Oxyhemoglobin