Coordination Compounds

COORDINATION COMPOUNDS
Coordination compounds refer to particular class of compounds in which the
central atom or ion, usually a metal, is surrounded by cluster of ions or molecules.
Addition Compounds
It is a matter of common observation, that when two or more stable
compounds are allowed to combine together in stoichiometric proportions these result
in the formation of crystalline substances called molecular or addition compounds. A
few examples are given below:
a)KCl + Mg Cl2 + 6H2O KCl. Mg Cl2 . 6H2O
b) CuSO4 + 4NH3 CuSO4 . 4NH3C) Fe(CN)2 + 4KCN  Fe(CN)2 .4KCN

These addition compounds fall into two categories, namely; double salts and co-
ordination compounds.
a) Double Salts:
These are the addition compounds which are stable in the solid state but break up
into its constituents in dissolved state. In such compounds the individual properties of
the constituents are not lost. For example, an aqueous solution of carnallite
(KCl. MgCl2. 6H2O) shows the properties of K+,Mg+2 and Cl – ions)

b) Coordination Compounds:
These are the addition compounds which retain their identity in the solid as well as
in the dissolved state. In such compounds the individual properties of the constituents
are usually lost. For example,
Complex ions such as [Fe(CN)6]4-of K4 Fe (CN)6, do not dissociate intoFe2+ and
CN – ions in solution.

Werner theory of co-ordination compounds

Postulates
1. There are two types of valencies shown by central metal/metal ion in a compound
primary and secondary.
2. Primary valency corresponds to oxidation number and secondary valency
corresponds to co-ordination number.
3. Primary valency is satisfied by negative ions (atoms) while secondary valency is
satisfied by ligands which can be neutral and as well as negative.

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i.e. anions can satisfy prim as well as secondary valencies while neutral groups can
satisfy only secondary valency .

4. Ligands/ions attached by secondary valency do not ionize while ions attached by

primary valency ionize K4 [Fe(CN)4].
5. The secondary valencies are directional and are responsible for the isomerism in
complexes as well as its spatial arrangement .

a) Coordination Entity:
A coordination entity constitutes a central metal atom or ion bonded to a fixed
number of ions or molecules. For example, [CoCl3 (NH3)3]

b) Complex:
A complex ion is an electrically charged radical or species, carrying positive or
negative charge in which the central atom or ion is surrounded by a suitable number of
neutral molecules or negative ions (called ligands). Some common examples are:
[Ni(NH3)6]2+,[Co (NH3)4]2+, [Pt Cl6]2-,[Ag(CN)2 ]-
The complex ion carrying a positive charge is called cationic complex, the one
with a negative charge is called anionic complex and the one with no charge is called a
neutral complex.
The salts of the complex ions are called complex compounds or coordinate
compounds.

c) Central atom/ion:
In a coordination entity, the atom/ion to which a fixed number of ions/groups are
bound in a definite geometrical arrangement around it is called the central atom or ion.
For example, the central atom/ion in the coordination entities:
[NiCl2(H2O)4], [CoCl(NH3)5]2+ and [Fe(CN)6]3- are Ni2+, Co3+ and Fe3+,
respectively. These central atoms/ ions are also referred to as Lewis acids.

d) Ligands :
The ions or molecules bound to the central atom/ion in the coordination entity are
called ligands. These may be simple ions such as Cl ,neutral molecules such as H2O or
NH3.
The ligands are capable of donating an electron pairs to a central metal ion. Thus,
ligands is a Lewis base.

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e) A ligand may contain one or more donor sites. Depending upon the number of
donor sites, the ligands may be classified as:

1. When a ligand is bound to a metal ion through a single donor atom as with Cl - ,
H2O or NH3. The ligand is said to be unidentate.
2. Di or bidentate:When a ligand can bind through two donor atoms as in H2NCH2
CH2NH2 (ethane-1,2-diamine) or C2O42- (oxalate), the ligand is said to be didentate.
3. Multidentate ligands: When several donor atoms are present in a single ligand as
in N(CH2CH2NH2)3, the ligand is said to be polydentate.
Ethylenediaminetetraacetate ion (EDTA4-) is an important hexadentate ligand. It
can bind through two nitrogen and four oxygen atoms to a central metal ion.
4. Ligands which can bond (ligate) to the central atom/ion through two different
atoms present in it are called ambidentate ligands.
But at a time, only one is linked to central metal atom eg.
 NO2-: The NO2- ion can coordinate to the central atom/ion either through the N
atom or through the O atom. M  NO2 or M  O – N = 0.
 SCN -: The SCN – ion can coordinate to the central atom/ion either through the S
atom or through the N atom. M  SCN or M  NCS.

f) Denticity and chelation (Chelating Ligands):

When a multidentate ligand simultaneously coordinates to a metal ion by more than
one donor site, then a ring – like structure is obtained. It is called a chelate ring and the
ligand is known as chelating ligand (from Greek word chele meaning claw). The
number of such ligating groups indicate the denticity of the ligand.

g) Coordination number:
The coordination number [CN] of a metal ion in a complex can be defined as the
number of ligand donor atoms to which the metal is directly bonded.
For example, In the complex ions, [Pt Cl6]2- and [Ni (NH3)4]2+, the coordination
number of Pt and Ni are 6 and 4 respectively.
Similarly, in the complex ions, [Fe(C2O4)3]3- and [Co (en)3]3+, the coordination
number of both, Fe and Co is 6 because C 2 O42- and en (ethane -1,2- diamine) are
didenatate ligands.
It is important to note here that co-ordination number of the central atom/ion is
determined only by the number of sigma bonds formed by the ligand with the central
atom/ion.

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Pi bonds, if formed between the ligand and the central atom/ion, are not counted
for this purpose.
h) Coordination sphere:
The central atom/ion and the ligands attached to it are enclosed in square
bracket and is collectively termed as the coordination sphere.

i) The ionisable groups are written outside the bracket and are called counter ions.
For example, in the complex K4 [Fe(CN)6] the coordination sphere is [Fe(CN)6]4-
and the counter ion is K.

j) Co-ordination polyhedron:
The spatial arrangement of the ligand atoms which are directly attached to the
central atom/ion defines a coordination polyhedron about the central atom.
The most common coordination polyhedra are octahedral, Square planar and
tetrahedral.
For example, [Co(NH3)6]3+ is octahedral, [Ni(CO)4] is tetrahedral and [PiCl4]2-
is square planar.

k) Oxidation number of central atom:

The oxidation number of the central atom in a complex is defined as the charge
it would carry if all the ligands are removed along with the electron pairs that are
shared with the central atom.
The oxidation number is represented by a Roman numeral in parenthesis following the
name of the coordination entity.
For example, oxidation number of copper in [Cu(CN)4]3- is +1 and it is written as
Cu(I).

l) Homoleptic and heteroleptic complexes:

Complexes in which a metal is bound to only one kind of donor groups, e.g.,
[CoCl6] are known as homoleptic complexes .
Complexes in which a metal is bound to more than one kind of donor groups,
e.g., [Co((NH3)4Cl2]+ are known as heteroleptic complexes.

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Formulas of Mononuclear Coordination Entities

Mononuclear coordination entities contain a single central metal atom. The
following rules are applied while writing the formulas:
a) The central atom is listed first.
b) The ligands are then listed in alphabetical order (according to name of ligand). The
placement of a ligand in the list does not depend on its charge.
c) Polydentate ligands are also listed alphabetically. In case of abbreviated ligand, the
first letter of the abbreviation is used to determine the position of the ligand in the
alphabetical order.
d) The formula for the entire coordination entity, whether charged or not, is enclosed
in square brackets. When ligands are polyatomic, their formulas are enclosed in
parenthesis. Ligand abbreviations are also enclosed in parenthesis.
e) There should be no space between the ligands and the metal with in a co-ordination
sphere.
f) When the formula for a charged coordination entity is to be written without that of
the counter ion, the charge is indicated outside the square brackets as a right
superscript with the number before the sign. For example, [Co(CN) 6]3-,
[Cr(H2O)6]3+ etc.
g) The charge of the cation(s) is balanced by the charge of the anion(s) in complex
compound.

Naming of Mononuclear Co-ordination Compounds

The following rules are used when naming coordination compounds:
a) The cation is named first in both positively and negatively charged coordination
entities.
b) The ligands are named in an alphabetical order before the name of the central
atom/ion. (This procedure is reversed from writing formula).
c) Names of the anionic ligands end in-o, those of neutral and cationic ligands are the
same except aqua for H2O, ammine for NH3,carbonyl for CO and nitrosyl for NO.
These are placed within enclosing marks( ). SO42- - Sulphato.
F− Fluorido NO3− Nitrato NO2− Nitrito –N –
− − − Nitrito –O-
Cl Chlorido OH Hydroxo ONO
Br − Bromido O 2− Oxo SCN − Thiocyanato – S-
I − Iodido C 2 O42− Oxalate NCS − Thiocyanato – N-
−
CN cyano CO2− 3
Carbonato

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For most neutral ligands the name of the molecule is used. The four common
exceptions are aqua (H2O), ammine (NH3), carbonyl (CO) and nitrosyl (NO).

d) Prefixes mono, di, tri etc. are used to indicate the number of the individual ligands
in the co-ordination entity. When the names of the ligands include a numerical
prefix then the terms bis, tris are used, the ligand to which they refer being placed
in parenthesis.
e) Oxidation state of the metal in cation, anion or neutral coordination entity is
indicated by Roman numeral in parenthesis.
f) If the complex ion is a cation, the metal is named same as the element. For
example, Co in a complex cationic called is called cobalt and Pt is called platinum.
g) If the complex ion is an anion, the name of the metal ends with the suffix – ate. For
example, Co in a complex anion, [Co (SCN)4]2- is called cobaltate. For some
metals, the Latin names are used in the complex anions, e.g., ferrate for Fe.
h) The neutral complex molecule is named similar to that of the complex cation. Ag-
Argentate , Sn- Stannate , Pb- Plumbate , Au- Aurate , Cu- Cuprate .

Questions
1. Write the formulas for the following co-ordination compounds:
a) Tetraammineaquachloridocobalt (III) Chloride
b) Potassium tetrahydroxozincate (II)
c) Potassium trioxalatoaluminate (III)
d) Dichloridobis(ethane-1, 2 – diamine) cobalt (III)
e) Tetracarbonylnickel (0).

2. Write the IUPAC names of the following co-ordination compounds:

a) [Pt (NH3)2 Cl (NO2)]
b) K3[Cr(C2O4)3]
c) [CO Cl2(en)2] Cl
d) [Co(NH3)5(CO3)] Cl
e) Hg[Co(SCN)4]

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

4. [Co(H2NCH2CH2NH2)3]2(SO4)3 is named as:

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5. [Ag (NH3)2] [Ag(CN)2 ] is named as:

6. Write the formulas for the following coordination compounds:

a) Tetraamminediaquacobalt (III) Chloride
b) Potassium tetracyanonickelate (II)
c) Tris(ethane-1,2- diamine) chromium (III) Chloride
d) Amminebromidochloridonitrito – N – Platinate (II)
e) Dichloridobis(ethane-1,2- diamine) platinum (IV) nitrate
f) Iron (III) hexacyanoferrate (II)

7. Write the IUPAC names of the following co-ordination compounds:

a) [Co(NH3)6]Cl3
b) [Co(NH3)5Cl]Cl2
c) K3[Fe(CN)6]
d) K3[Fe(C2O4)3]
e) K2[PdCl4]
f) [Pt (NH3)2Cl(NH2CH3)] Cl

8. Specify the oxidation numbers of the metals in the following co-ordination

entities:
a) [Co(H2O) (CN) (en)2 ]2+
b) [CoBr2(en)2]+
c) [Pt (Cl4)2+
d) K3[Fe(CN)6]
e) [Cr(NH3)3Cl3]

9. Using IUPAC norms write the formulas for the following:

a) Tetrahydroxozincate(II) ion
b) Potassium tetrachloridopalladate (II)
c) Diamminedichloridoplatinum (II)
d) Potassium tetracyanonickelate (II)
e) Pentaamminenitrito – O – cobalt (III)
f) Hexaamminecobalt (III) sulphate
g) Potassium tri(oxalate) chromate (III)
h) Hexaammineplatinum (IV)
i) Tetrabromidocuprate (II)
j) Pentaamminenitrito – N – cobalt (III)
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10. Using IUPAC norms write the systematic names of the following:
a) [Co (NH3)6] Cl3
b) [Pt (NH3)2 Cl (NH2CH3)] Cl
c) [Ti (H2O)6]3+
d) [Co (NH3)4Cl (NO2)]Cl
e) [Mn (H2O)6]2+
f) [NiCl4]2+
g) [Ni(NH3)6]Cl2
h) [Co(en)3]3+
i) [Ni (CO)4]

Isomerism in Coordination Compounds

The two or more chemical compounds with identical chemical formula but
different structures are called isomers, and the phenomenon is known as isomerism.

A. Structural Isomerism
This type of isomerism arises due to the difference in structures of coordination
compounds. It may be further subdivided into different types as follows:

a) Ionization Isomerism
This type of isomerism occurs when the counter ion in a coordination compound is
itself a potential ligand. As a result the counter ions and the ligand can change their
places. The following pairs of compounds are examples of ionization isomers.
[Co(NH3)5Br]2+ SO42- and [Co (NH3)5 SO4]+Br -
Pentaamminebromidocobalt (III) sulphate (violet) Pentaamminesulphato cobalt(III) bromide –(Red)
The violet compound, in aqueous solution, gives a precipitate with BaCl2 and not with
AgNO3 solution whereas the red compound gives a precipitate with
AgNO3 solution and not with BaCl2 solution.

b) Solvate Isomerism
This form of isomerism is known as ‘hydrate isomerism’ in case where water is
involved as a solvent. This is similar to ionization 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.
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An example is provided by the aqua complex [Cr(H2O)6]Cl3 (violet) and its
solvate isomer [Cr(H2O)5 Cl]Cl2. H2O (grey – green) and (Cr(H2o)4Cl2]Cl. 2H2O (dark
green).

c) Linkage Isomerism
This type of isomerism occurs in those complex compounds which contain
ambidentate ligands such as SCN-, NO2-, etc. These ligands have two donor atoms.
However, at a time only one is linked to the central metal atom of the complex,
e.g.[CO(NH3)5(NO2)] Cl2 (Yellow) and [CO(NH3)5(ONO)]Cl2 (red).
Another 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.

d) Coordination Isomerism
This type of isomerism is possible when both positive and negative ions of a
salt are complex ions and the two isomers differ in the distribution of ligands in the
cation and anionic co-ordination entity.
Some important examples are: (i) [CO(NH3)6] [Cr(CN)6] and [Cr(NH3)6}
[CO(CN)6]. This type of isomerism arises from the interchange of ligands between
cationic and anionic entities of different metal ions present in a complex.

B. Stereo-isomerism
These are the isomers in which the atoms are bonded to each other in same
order but differ in the precise arrangement of these atoms in space.

Geometric Isomerism
This type of isomerism arises in heteroleptic complexes due to different possible
geometric arrangements of the ligands in co-ordination entity. Important examples
of this behavior are found with coordination numbers 4 and 6.

a) In a square planar complex of formula [MX2 L2](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 e.g.(cis and trans) of [Pt (NH3)2Cl2]
 Such isomerism is not possible for a tetrahedral geometry.

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b) Similar behavior is possible in octahedral complexes of formula [MX 2 L4]in which
the two ligands X may be oriented cis or trans to each other. Geometrical isomers
(cis and trans) of [Co (NH3)4Cl2]+.
c) This type of isomerism also arises when didentate ligands L-L [e.g.,
NH2CH2CH2NH2(en)] are present in complexes of formula [MX 2(LL)2] e.g.
Geometrical isomers (cis and trans) of [CoCl2(en)2].
d) 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) isomers e.g. The facial (fac) and meridional (mer)
isomers of [Co(NH3)3(NO2)3].
e) Geometric isomers differ in their physical characteristics, out of which dipole
moments and visible /UV spectra are important.

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
are called chiral. The two forms are called dextro (d) and laevo (l) depending upon the
direction they rotate the plane of polarized light in a polarimeter (d rotates to the right,
l to the left).

a) In CN- 6, octahedral complexes. Compounds containing three bidentate ligands,

two bidentate and two monodentate ligands show optical isomerism. E.g
complexes like. (i) [M(AA)3] e.g., [Cr (Ox)3]3-, [CO (en)3]3+(ii) [M(AA)2 B2] e.g.
[Pt cl2 (en)2] 2+
Questions
1. Draw the possible structures of optical isomers of (a) [Cr(Ox)3]3- (b) [Pt
Cl2(en)2]2+.

2. Draw all the isomers geometrical and optical of (a) [Co Cl2(en)2]+.
(b) [Co Cl(en)2NH3]2+(c) [Co Cl3 (NH3)3] (d) [Cr Cl2(en) (NH3)2]+.

3. What are the basic difference between the two geometrical isomers-cis/trans
or fac/mer.

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Ans:-Geometrical isomers differ in their physical properties especially in showing
different dipole moment, UV and visible spectra.

4. What is a racemic mixture?

Ans:-The mixture having both dextro and laevo optical isomers in 1:1 ratio are called
racemic mixture.

5. What is speciality of racemic mixtures?

Ans:-Racemic mixtures () shows zero net rotation of plane of polarized light due to
external compensation.

6. What is the coordination number of central metal ion in [Co(NH 3)3Cl3) and
[Fe (C2O4)3]-3?

7. A coordination compound has the formula CoCl3.4NH3. It does not liberate

ammonia but precipitates chloride ions as silver chloride. Give the IUPAC
name of complex and write its structural formula.

8. How many ions are formed by [Co(NH3)6] Cl3 in aqueous solution?

9. The molar conductance of PtCl4. 4NH3 in water corresponds to a total of three

ions. Write its structure on the basis of Werner’s theory and also write its
IUPAC name.

10. The complex [Co(NH3)5 Br] SO4 gives white precipitates with BaCl2 solution
while [Co (NH3)5SO4] Br gives yellow precipitate with Ag NO3 solution.
Explain.

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Valence Bond (VB) Theory

The silent features of the theory are summarized below:
1. The central metal ion has a number of empty orbitals for accommodating electrons
donated by the ligands. The number of empty orbitals is equal to the co-ordination
number of the metal ion for the particular complex.
2. The atomic orbitals (s, p or d) of the metal ion hybridize to form hybrid orbitals
with definite directional properties. These hybrid orbitals now overlap with the
ligand orbitals to form strong chemical bonds.
3. The d-orbitals involved in the hybridization may be either inner (n-1) d-orbital or
outer n d-orbitals. The complexes formed in these two ways are referred to as low
spin and high spin complexes, respectively. Each ligand contains a lone pair of
electrons.
4. A covalent bond is formed by the overlap of a vacant hybridized metal orbital and
filled orbital of the ligand.
5. If the complex contains unpaired electrons, it is paramagnetic in nature, while if it
does not contain unpaired electrons, it is diamagnetic in nature.
6. The number of unpaired electrons in the complex points out the geometry of the
complex and vice – versa. In practice, the number of unpaired electrons in a
complex is found from magnetic moment measurements.
7. Under the influence of a strong ligand, the electrons can be forced to pair up
against the Hund’s rule of maximum multiplicity.
Weak ligands:-

𝐈 − < Br − < 𝐒 𝟐− < 𝐒𝐂𝐍− < 𝐂𝐥− < 𝐅 − < 𝐎𝐇 − < 𝐂𝟐 𝐎𝟒 𝟐− < 𝐎𝟐− < 𝐇𝟐 𝐎
< 𝐌𝐂𝐒 − < pyridine (p), NH3< CN-< CO strong ligands.
Questions
1. Explain on the basis of valence bond theory, the experimental findings that
[Ni(CN)4]2- ion with a square –planar structure is diamagnetic and the
[NiCl4]2- ion with tetrahedral geometry is paramagnetic.

2. Both [Ni(CO)4] and [NiCl4]-2 possess sp3hybridisation but they differ in their
magnetic behavior. Explain.

3. [Fe(CN)6 ]-4 is diamagnetic while [Fe(CN)6]-3 is paramagnetic. Explain with the

help of VBT.

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4. Potassium ferrocyanide is diamagnetic whereas potassium ferricyanide is
paramagnetic. Explain.
5. [Fe(H2O)6]+3 is strongly paramagnetic whereas [Fe(CN)6]-3 is weakly
paramagnetic .explain.
6. Account for: [Ni(CO)4] has tetrahedral geometry whereas [Ni(CN)4]-2 has
square planar geometry.
7. [Ni(CO)4] possesses tetrahedral geometry while Pt(NH3)2Cl2 square planar
why?

Magnetic Properties of Co-ordination Compounds

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 hybridization with 4s
and 4p orbitals. The magnetic behavior 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 hybridization 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. The magnetic data agree with maximum spin pairing
in many cases, [Mn(CN)6]3- and [Co(C2O4)3]3- are inner orbital complexes involving
d2sp3hybridisation, the former two complexes are paramagnetic and the latter
diamagnetic.
On the other hand, [MnCl6]3- and [CoF6]3- are outer orbital complexes involving
sp3d2 hybridization and are paramagnetic corresponding to four and four unpaired
electrons.

Limitations of Valence Bond Theory

While the VB theory, to a larger extent, explains the formation, structures and
magnetic behavior of coordination compounds, it suffers from the following
shortcomings:
a) It involves a number of assumptions.
b) It does not give quantitative interpretation of magnetic data.
c) It does not explain the colour exhibited by co-ordination compounds.
d) It does not give a quantitative interpretation of the thermodynamic or kinetic
stabilities of co-ordination compounds.
e) It does not make exact predictions regarding the tetrahedral and a square planar
structures of 4 co-ordinate complexes.
f) It does not distinguish between weak and strong ligands.
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Crystal Field Theory

The crystal field theory (CFT), makes the following assumptions
1. The ligands are assumed to be point charges.
2. The interactions between the point charges and the electrons of the central metal
are electrostatic in nature.
3. The five d-orbitals of metal can be divided into two groups depending upon the
nature of their orientation in space.
a) The three d-orbitals (dxy, dyz, dzx) which orient in the regions in between the
coordinate axis are designated as t2g orbitals.
b) The two other orbitals (dx2-y2 and dz2) which orient along the axis are labeled as e g
orbitals.
4. In the case of a free ion or in a isolated gaseous metal atom/ion all the five d-
orbitals have the same energy i.e., they are degenerate meaning energetically alike.
This degeneracy is maintained if a spherically symmetrical field of negative
charges surrounds the metal atom/ion.
5. However, when this negative field is due to ligands (either anions or negative ends
of polar molecules like H2O, NH3etc) in a complex, it becomes asymmetrical and
the degeneracy of the d-orbitals is lifted.

A. Crystal Field Splitting in Octahedral Coordination Entities

a) In an octahedral coordination entity with six ligands surrounding the metal
atom/ion, there will be repulsion between the electrons in metal d –orbitals and the
electrons (for negative charges) of the ligands.
b) Such a repulsion is more when the metal d orbital is directed towards the ligand
than when it is away from the ligand.
c) Thus, the dx2-y2 and dz2 orbitals (eg) which point towards the axis along the
direction of the ligand will experience more repulsion and will be raised in energy
and the dxy, dyz and dxz orbitals t2g which are directed between the axis will be
lowered in energy relative to the average energy in the spherical crystal field. Thus,
the degeneracy of the d-orbitals has been removed due to ligand electron-metal
electron repulsions in the octahedral complex to yield three orbitals of lower
energy, t2g set and two orbitals of higher energy, eg set.

This splitting of the degenerate levels due to the presence of ligands in a

definite geometry is termed as crystal field splitting and the energy separation
is denoted by o (the subscript o is for octahedral). Thus, the energy of the two
eg orbitals will increase by (3/5) o and that of the three t2g will decrease by (2/5)o.
The crystal field splitting o, 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

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in small splitting of d orbitals. In general ligands can be arranged in series in the order
of increasing field strength as given below:
𝐈 − < Br − < 𝐒𝐂𝐍 − < 𝐂𝐥− < 𝐅 − < 𝐎𝐇 − < 𝐂𝟐 𝐎𝟒 𝟐− < 𝐇𝟐 𝐎
< 𝐍𝐂𝐒 − < edta4− NH3<en-<CN -<CO
Such a series is termed as spectrochemical series. It is an experimentally
determined series.
 Electronic Configuration for different dn entities:
This single d1- electron occupies one of the lower energy t2g orbitals. In d2 and
d3 coordination entities, the d electrons occupy the t 2g orbitals singly in accordance
with the Hund’s rule(𝐢. 𝐞. 𝐭 𝟐 𝟏𝐠 , 𝐭 𝟐 𝟐𝐠 , 𝐭 𝟐 𝟑𝐠 𝐫𝐞𝐬𝐩. ).
For d4 ions, two possible patterns of electron distribution arise: (i) the fourth
electron could either enter the t2g level and pair with an existing electron, or (ii) it
could avoid paying the price of the pairing energy by occupying the e g level.
Which of these possibilities occurs, depends on the relative magnitude of the crystal
field splitting, o and the pairing energy, P (P represents the energy required for
electron pairing in a single orbital). The two options are:
a) If o<P, the fourth electron enters one of the e g orbitals giving the configuration
t 2 3g e1g . Ligands for whicho<P are known as weak field ligands and form high spin
complexes.
b) If o>P, it becomes more energetically favourable for the fourth electron to occupy
a t2g orbital with configuration t2g4 eg0. Ligands which produce this effect are known
as strong field ligands and form low spin complexes.
Calculations show that d4 to d7 coordination entities are more stable for strong
field as compared to weak field cases.

B. Crystal Field Splitting in Tetrahedral Coordination Entities

In tetrahedral coordination entity formation, the 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 t = (4/9) 0. Consequently, the orbital splitting energies are not
sufficiently large for forcing pairing and, therefore, low spin configurations are rarely
observed i.e. most of the Td complexes are high spin.

Colour in Coordination Compounds

One of the most distinctive properties of transition metal complexes is their
wide range of colours. This means that some of the visible spectrum is being removed
from white light as it passes through the sample and the colour of the complex is
complementary to that which is absorbed.

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Relationship between the wavelength of light absorbed and the colour observed
in some Co-ordination Entities:
Co-ordination Wavelength of Colour of light Colour of
entity light absorbed absorbed coordination
(nm) entity
[Co Cl(NH3 )5 ]2+ 535 Yellow Violet
[Co (NH3 )5(H2 O)] 3+ 500 Blue green Red
[Co (NH3 )6] 3+ 475 Blue Yellow orange
[Co (CN)6 ]3− 310 Ultraviolet Pale yellow
[Cu (H2O)4 ] 2+ 600 Red Blue
[Ti (H2 O6)]3+ 498 Blue green Purple

The colour in the coordination compounds can be readily explained in terms of

the crystal field theory:
 Consider, for example, the complex [Ti(H2O6)]3+, which is violet in colour. This is
an octahedral complex (Ti3+ is a 3d1 system).
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 e g level (𝐭 𝟐 𝟏𝐠 e0g →
𝐭 𝟐 𝟎𝐠 e1g ). Consequently, the complex appears violet in colour.
 In simple words according to crystal field theory the colour of the coordination
compounds arises due to d-d transition of the electron.
 The colour of a particular compound depends upon the magnitude of , the crystal
field splitting which is further found to be dependent upon:
a) Nature of the metal ion.
b) Oxidation state of metal ion.
c) Nature of ligand: A stronger ligand has higher splitting power than a weak ligand.
d) Geometry of complex. The value of t is  50% as large as that of 0.

 It is important to note that in the absence of ligand, crystal field spitting does not
occur and hence the substance is colourless. For example
a) Removal of water from [Ti(H2O6)]Cl3 on heating renders it colourless.
b) Similarly, anhydrous CuSO4 is white, but CuSO4.5H2O is blue in colour.
c) The influence of the ligand on the colour of a complex may be illustrated by
considering the complexes, 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 colour changes occur:
[Ni(H2O6)]2+(aq) green,[Ni(H2O)4(en)]2+(aq) pale blue ,[Ni(H2O)2(en)2]2+(aq)
blue/purple , [Ni(en)3]2+(aq) Violet.

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Limitations of Crystal Field Theory

The crystal field model is successful in explaining the formation, structures,
colour and magnetic properties of coordination compounds to a large extent.
a) However, from the assumptions that the ligands are point charges, it follows
that anionic ligands should exert the greatest splitting effect. The anionic
ligands actually are found at the low end of the spectrochemical series.
b) Further, it does not take into account the covalent character of bonding between
the ligand and the central atom.

Stability of Coordination Compounds in Solution

The stability of a complex in solution refers to the degree of association
between the two species involved in the state of equilibrium.
For a reaction of the type: M + 4L ⇄ ML4 we can write the overall
stability constant thus: 4 = [ML4]/[M][L]4.
The stepwise and overall stability constant are therefore related as follows:
4 = K1K2 K3 K4

In general, higher is the value of stability constant for a complex ion greater will be its
stability. Alternatively, 1/K values are sometimes called instability constant or
dissociation constant.

1. Calculate the overall complex dissociation equilibrium constant for the

𝐂𝐮(𝐍𝐇𝟑 )𝟐+ 13
𝟒 𝐢𝐨𝐧, given that B4 for this complex is 2.110 .
Ans:- Formation of [Cu(NH3)4 ]2+ involves following steps
Cu2+ + NH3 ⇌ [Cu(NH3 )]2+ , K1 = [Cu(NH3 )]2+ /[Cu2+ ][NH3 ]
[Cu(NH3 )]2+ + NH3 ⇌ [Cu(NH3 )2 ]2+ , K 2 = [Cu(NH3 )2 ]2+ /[Cu(NH3 )]2+ [NH3 ]

[Cu(NH3 )]2+ + NH3 ⇌ [Cu(NH3 )3 ]2+ , K 3 = [Cu(NH3 )3 ]2+ /[Cu(NH3 )2 ]2+ [NH3 ]

[Cu(NH3 )]2+ + NH3 ⇌ [Cu(NH3 )4 ]2+ , K 4 = [Cu(NH3 )4 ]2+ /[Cu(NH3 )3 ]2+ [NH3 ]

Further, 4 = K1 K2 K3 K4

K1, K2, K3and K4 are stepwise stability constants and B4 is overall stability
constant.
1
Further, overall dissociation constant =
overall stability constant
1
Given 4 = 2.11013 . Thus, overall dissociation constant = = 4.710−14
2.11013

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Factors affecting the stability of complex

The stability of a complex depends upon
1. Nature of Central ion: The term nature means the charge density on the central
ion i.e., greater is the charge density more is the stability of a Complex. For
example, out of complexes of Fe2+ and Fe3+ those of Fe3+ are more stable.
[Fe(CN)6]4-; K = 1.8 106.

2. Nature of Ligand:
Chelate Effect: Complexes containing chelate rings are usually more stable than
similar complexes containing no rings. This is termed as chelate effect.
The complexes which are formed by chelating ligands like ethylene diamine
(en), EDTA, etc. are more stable than those formed by monodentate ligands such as
H2O or NH3.
Questions
1. Discuss briefly giving an example in each case the role of co-ordination
compounds in (i) biological systems (ii) analytical chemistry (iii) medicinal
chemistry and (iv) extraction/metallurgy of metals.
Ans:- (1) Role of coordination compounds in biological systems:-
a) Haemoglobin and myoglobin are complex entities of iron (II) which stores
oxygen in a regulator of respiration.
b) Chlorophylls are complex compounds of magnesium. In chlorophyll, Mg is
coordinated to four N- atoms of porphyrin units.
c) Vitamin B12 (cyanocobaltammine) is a complex of cobalt metal. It is very
important in synthesis of blood in the body and various other body functions.
d) Enzymes like carboxypeptides A and carbonic anhydrase act as catalysts in
biological system.
(2) Role of coordination compounds in analytical chemistry:-
a) The polydentate ligand, EDTA (ethylene diammine tetra acetate) is used in
determining hardness of water by simple titration method.
b) The detection of copper (II) involves the formation of a deep blue coloured
complex, [Cu(NH3)4]2+ on addition of ammonia solution to a solution of Cu2+
ion.
Cu2+ + 4NH3 [Cu(NH3)4]2+
Deep blue
(3) Role of coordination compounds in medicinal chemistry:
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 Coordination Compounds
a) EDTA is used in the treatment of lead poisioning.
b) Some coordination compounds of platinum (cis-platinum and related
compounds inhibit the growth of tumors and thus used in treatment of cancers.
(4) Role of coordination compounds in extraction/metallurgy of metals:
a) For the extraction of silver (Ag), formation of soluble cyanide complex is used
in extraction of metals like silver and gold. Silver ore Ag2S, is treated with
NaCN or KCN solution in presence of air to form a soluble complex, sodium
argento cyanide from which silver metal is precipited by adding zinc scrap.
AgS + 4NaCN  2Na [Ag(CN)2] + Na2S
2Na [Ag(CN)2]+Zn  Na2 [Zn(CN)4] + 2Ag
Sodiumtetracyno zincate(II) silver
b) Similarly, gold is leached with NaCN or KCN and a soluble complex of gold is
formed. 4Au+ 8KCN + 2H2O + O24K[Au(CN)2] + 4 KOH
Potassium dicyno gold (I)
Heat
2[Au(CN)2 ]− → [Zn(CN)4 ]2− +2Au ↓
c) Coordination compound of Ag and Au are used as the constituents of
electroplating baths for controlled delivery of Ag + and Au+ ions.

2. Predict the number of unpaired electrons in the square planar [Pt(CN)4]2-

ion.
Ans:-Pt2+ is a d8 ion. For square – planar geometry dsp2 hybrids are required. For
the availability of one d – orbital, pairing of electrons takes place in the remaining
d – orbitals. Hence , there are no unpaired electrons in [Pt(CN)4]2- ion.

3. [Co(NH3)6]-3 and [CoCl6]3- both have octahedral geometry ,then what is the
difference between the two?
Ans:-[Co(NH3)6]-3 is an inner orbital or low spin complex with d2sp3 hybridization
while in [CoCl6]3- is an outer orbital or high spin complex with sp3d2 hybridization.
4. Aqueous copper sulphate solution (blue in colour) gives:
a) A green precipitate with aqueous potassium fluoride, and
b) A bright green solution with aqueous potassium chloride. Explain these
experimental results.
Ans:- We know that aqueous CuSO4 solution exist as [Cu(H2O)4] SO4 which give
the bluecolour due to formation of [Cu(H2O)4]2+ ions.
a) When KF is added, the weak H2O ligands replaced by F- ligands and formed
[CuF4]2- ion [Cu(H2O)4]2- + 4F –→ [CuF4]2- +4H2O
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 Coordination Compounds
Tetrafluorocuprate(II) ion (Green ppt)
b) When KCl is added, the weak H2O ligands replaced by Cl – ligands and formed
[CuCl4]2- ion [Cu (H2O)4]2- + 4Cl-→ [CuCl4]2- + 4H2O
Tetrachlorocuprate (II) ion (Green solution)

5. What is the coordination entity formed when excess of aqueous KCN is

added to an aqueous solution of copper sulphate? Why is it that no
precipitate or copper sulphate is obtained when H2S (g) is passed through
this solution?

Ans:-CuSO4 + 4KCN → K2 [Cu(CN)4] + K2SO4

In K2[Cu(CN)4], the Cu+2 ions are present in the coordination entity, so aqueous
solution does not contain Cu2+ ions, during this reaction when H2S(g) passed
through this solution no precipitate of CuS is formed.

6. What is spectrochemical series? Explain the difference between a weak

field ligand and a strong field ligand.

Ans:-Ligands have different field strengths and as a result the crystal field
splitting, 0 or t depends upon the field produced by the ligand and charge on
metal ions. 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.

The arrangement of the ligands in order of increasing field strength is known as

spectrochemical series.

𝐈 − < Br − < 𝐒𝐂𝐍 − < 𝐂𝐥− < 𝐒 𝟐 < 𝐅 − < 𝐎𝐇 − < 𝐂𝟐 𝐎𝟒 𝟐− < 𝐇𝟐 𝐎
< 𝐞𝐝𝐭𝐚𝟒− NH3<en-< CN -< CO

7. What is crystal field spitting energy?

Ans:-In an octahedral coordination entity due to repulsion between the electrons in

metal d-orbitals and the electrons (or negative charges) of the ligands, the
degeneracy of d-orbitals is lost and they split up into two levels of different energy.
The spitting of degenerate levels is termed as crystal field splitting and the
difference of energy between these levels is known as CFSE (Crystal Field splitting
energy). It is denoted as 0.
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 Coordination Compounds
4- 2+
8. [Fe(CN)6] and [Fe(H2O)6] are different colours in dilute solutions: why?

Ans:-In both the complexes the ligand cyanide ion and water molecules exert
different ligand fields. As a result of it the magnitude of crystal field splitting
energy, 0 is different. Accordingly different component of the visible light
(VIBGYOR) shall be absorbed and therefore the transmitted colour would be
different i.e., the colour of complexes would be different.

9. What will be the correct order of the wavelengths of absorption in the

visible region for the following (a) [Ni(NO 2)6]4+ (b) [Ni(NH3)6]2+(c)
[Ni(H2O)6]2+.

Ans:- (a) The order of the ligand in the spectrochemical series: H2O < NH3< No2-
Hence the wavelength of the light observed will be in the order:

[Ni(H2O)6]2+< [Ni(NH3)6]2+< [Ni(NO2)6]4-

Thus wavelengths absorbed (E = hc/) will be in the opposite order.

10. Amongst the following, the most stable complex is:

(a) [Fe(H2O)6]3+ (b) [Fe(NH3)6] (c) [Fe(C2O4)]3- (c) [Fe(Cl)6]3-

Ans:-(c) Oxalate ion C2O42- is a chelating ligand and hence shall form more stable
complex.

11. Amongst the following ions which one has highest magnetic moment?
(a) [Cr(H2O)6]3+ (b) [Fe(H2O)6]2+ (c) [Zn((H2O)6]2+

Ans:-(b) All the three complexes are octahedral, outer orbital and high spin
complexes. The configuration of chromium (III), Fe(II) and Zn(II)ions are:

Cr3+ : 3d3; Fe2+ : 3d6; Zn2+ : 3d10

Hence, Cr has three unpaired electrons, Fe has 4 unpaired electrons and Zn has no
unpaired electrons.

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CBSE EXAMINATION QUESTIONS

1. Write the IUPAC name of the complex [Cr(NH 3)4 Cl2]+. What type of isomerism
does it exhibit?
2. (i) Write down the IUPAC name of the following complex:
[Cr(NH3)2 Cl2(en)] Cl (en= ethylenediamine)
(ii) Write the formula for the following complex:
Pentaamminenitrito-o-Cobalt (III)
3. (a) Draw the geometrical isomers of complex [Pt(NH 3)2 Cl2].
(b) On the basis of crystal field theory, write the electronic configuration for d 4
ion if ∆0< P.
(c) Write the hybridization and magnetic behaviour of the complex [Ni(CO) 4].
(At. No. of Ni = 28)
4. (a) For the complex [Fe(CN)6]3-, write the hybridization type, magnetic character
and spin nature of the complex. (At. Number: Fe = 26).
(b) Draw one of the geometrical isomers of the complex [Pt (en) 2Cl2]2+ which is
optically active.
5. When a coordination compound CrCl3. 6H2O is mixed with AgNO3, 2 moles of
AgCl are precipitated per mole of the compound. Write
(i) Structural formula of the complex.
(ii) IUPAC name of the complex.
6. (i) What type of isomerism is shown by the complex [Co(NH 3)6][Cr(CN6)]?
(iii) Why a solution of [Ni(H2O)6]2+ is green while a solution of [Ni(CN)4]2- is
colourless? (At. No. of Ni = 28).
Write the IUPAC name of the following complex: [Co(NH 3)5(CO3)] Cl.

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