UNIT 9

COORDINATION COMPOUNDS

c/3 After studying this unit thoroughly, the reader should be able to
• have an idea of the nature of coordination compounds and the basic concepts used in coordination chemistry;
P • learn the nomenclature of different types of coordination compounds;
Q • learn the different types of isomerism exhibited by coordination compounds;
£> • learn the nature of bonding in coordination compounds;
• discuss the stability of coordination compounds;
• have an idea of the applications of coordination compounds.

ransition metals possess a characteristic property important biological functions. For example, photosynthesis
T of undergoing complex formation. Due to in plants involves chlorophyll, which is a coordination
this remarkable tendency, they form a large number of
compound of magnesium. The red pigment haemoglobin
coordination compounds. Coordination compounds are not present in blood, which is responsible for the regulation of
only formed by transition elements but are also formed by respiration process in the animal world, is a coordination
several other non-transition metals although the tendency compound of iron. A variety of metallurgical processes,
is much less. The branch of chemistry which deals with the catalysts and analytical reagents make use of coordination
study of coordination compounds or complex compounds compounds. Therefore, the study of coordination compounds
is known as Coordination Chemistry. is highly significant from biological, industrial and analytical
Coordination compounds are widely distributed in points of view. In the forthcoming sections, \ye shall briefly
minerals, plants and animals and are known to play many study the chemistry of coordination compounds.

9.1 COORDINATION COMPOUNDS AND SOME IMPORTANT TERMS USED IN

COORDINATION CHEMISTRY
Coordination compounds are also known as complex
compounds or Werner complexes. A brief idea of the nature
of coordination compounds and the important terms used
in coordination chemistry are given below.
9.1.1 Coordination Compounds
Coordination compounds are those molecular or
addition compounds in which a central metal atom or ion
is permanently attached to certain atoms or groups of atoms
called ligands. The ligands are capable of donating atleast
a pair of electrons to the central metal atom or ion and get
attached to it by coordinate bonds.
Coordination compounds retain their identity even in
solution and their properties are different from those of
their constituent atoms or groups. For example, potassium
ferrocyanide, K4[Fe(CN)6] is a coordination compound. It
ionises in solution as
K4[Fe(CN)6] 4K+ + [Fe(CNJ6]4’
Pot.ferrocyanide Ferrocyanide ion
(complexion)
Ferrocyanide ion, [Fe(CN)6]4~ is the complex part of
this coordination compound. It consists of six cyanide ions
(ligands) permanently attached to the central Fe2+ ion. This
ion does not dissociate further in the solution and retains
its identity. Moreover, the properties of [Fe(CN)6]4~ ion are
quite different from those of Fe2+ and CN” ions.
The chemistry of coordination compounds started
with the brilliant work of Alfred Werner in 1892. This
is why Werner is regarded as the Father of coordination
chemistry and coordination compounds are usually
referred to as Werner complexes.
Difference between Double Salts and Coordination
Compounds
Both double salts as well as coordination compounds
are molecular or addition compounds and are formed by
the combination of two or more salts in stoichiometric (i.e.,
simple molecular) ratio. However, the two differ in their
ionisation behaviour in aqueous solutions as described
ahead.
Coordination Compounds
1. Double salts : Double salts are those molecular
or addition compounds which exist in the solid state but
dissociate into their constituent ions when dissolved in water.
Thus, double salts lose their identity in aqueous solutions.
Following examples illustrate the nature of double salts.
(i) Mohr’s salt, FeSO4 ■ (NH4)2SO4 • 6H2O is a double
salt and may be obtained by mixing the saturated solutions
of ferrous sulphate and ammonium sulphate and cooling
the resultant mixture.
FeSO4 + (NH4)SO4 + 6H2O ----- >
FeSO4 -(NH4)2SO4 • 6H2O
Mohr's salt
When dissolved in water, Mohr’s salt loses its identity
and dissociates into its constituent ions as follows.
FeSO4(NH4)2SO4 • 6H2O ----- >
Fe2+ + 2NH4 + 2SO4~ + 6H2O
The aqueous solution of this salt gives the test of Fe ,
i q_
NH4 and SO4 ions. Thus, Mohr’s salt is a double salt.
(ii) Potash alum, K2SO4 • A12(SO4)3 • 24H2O is another
example of a double salt. It may be obtained by mixing the
saturated solutions of potassium sulphate and aluminium
sulphate and evaporating the resultant solution.
K2SO4 + A12(SO4)3 + 24H2O
K2SO4 • A12(SO4)3 • 24H2O
Potash alum
When potash alum is dissolved in water, it loses its
identity and dissociates into its constituent ions as shown
below.
K2SO4 • A12(SO4)3 • 24H2O ----- >
2K+ + 2A13+ + 4SO4“
Thus, the solution of potash alum responds to the test
ofK+, Al3+ and SO2- ions.
Some other examples of double salts are carnallite
(KCl • MgCl2 • 6H2O), ferric alum
l(NH4)2SO4 • Fe2(SO4)3 • 24H2O], etc.
2. Coordination compounds : As described earlier,
coordination compounds are those molecular or addition
compounds which retain their identity in aqueous solutions
and show properties entirely different from those of their
constituent ions. Following examples illustrate the nature of
coordination compounds.
(i) Potassium ferrocyanide, K4[Fe(CN)6] is a
coordination compound and may be obtained by mixing
a solution of ferrous sulphate with a solution of KCN until
the precipitate of ferrous cyanide formed gets dissolved.
FeSO4 + 2KCN ----- > Fe(CN)2 + K2SO4
Ferrous cyanide
(ppt.)
483
Fe(CN)2 + 4 KCN ----- > K4[Fe(CN)6]
Pot. ferrocyanide
As explained earlier, it dissociates in solution as
follows.
K4[Fe(CN)6] 4K+ + [Fe(CN)6]4"
Ferrocyanide ion
The ferrocyanide ion is a complex ion and retains its
identity in solution. It does not dissociate further to give
Fe2+ and CN“ ions. Thus, an aqueous solution of potassium
ferrocyanide does not give the test of Fe2+ and CN“ ions.
(ii) Potassium tetracyanidonickelate (II),
K2[Ni(CN)4] is also a coordination compound and may
be obtained by dissolving the white precipitate of nickel
cyanide in the excess of potassium cyanide solution.
Ni(CN)2 + 2KCN ---- > K2[Ni(CN)4]
Potassium
tetracyanonickelate (II)
When dissolved in water, it dissociates as follows.
K2[Ni(CN)4] 2K+ + [Ni (CN)4]2~
Tetracyanonickelate
(II) ion
The tetracyanidonickelate (II) ion is a complex ion
and does not dissociate further into Ni2+ and CN~ ions.
Therefore, the aqueous solution of this complex does not
give the tests of Ni2+ and CN- ions.
----- >.
9.1.2 Some Important Terms Used in
Coordination Chemistry
The study of coordination compounds involves several
typical terms. These are described below.
1. Central metal atom or ion : The metal atom or ion to
which certain atoms or groups of atoms (called ligands) are
permanently attached in a coordination compound is called
+ 24H2O central metal atom or ion. For example, in the complex
K[Ag(CN)2], Ag* is the central metal ion.
Any metal atom or ion which can accept electrons
given by ligands can act as a central metal atom or ion
and can involve in complex formation. Complexes are
usually formed by transition metal atoms or ions because
they possess sufficient vacant d-orbitals to accommodate
electrons given by ligands.
2. Ligands : The molecular or ionic species which gets
directly attached to the central metal atom or ion during the
formation of a complex is called a ligand. For example,
in the complex K4[Fe(CN)6], CN~ ions are ligands because
they get directly attached to the central Fe2+ ion during the
formation of this complex.
Ligands attach to central metal atom or ion through
coordinate bonds. Therefore, the atoms, ions or molecules
which have a tendency to donate a pair of electrons to the
central metal atom can work as ligands. Ligands may be
both neutral as well as negatively charged. Some important
ligands are
 484 _____________________________________ ___
nh3, h2o :, — nh2, h2n—ch2—ch2—nh2, :f~: cN~etc.
(ethylene diamine, en)
3. Complex ion (Coordination entity) : The electrically
charged speciesformed by the union ofa central metal atom orion
with one or more ligands is called a complex ion. For example,
[Fe (CN)6]4~ ion is a complex ion. In this complex ion, the
central Fe ’’ ion is attached to six CN ligands. Similarly,
oi oi
[Cu (NH3)4] is a complex ion in which Cu ’r ion is linked
to four NH3 ligands.
A complex ion may have positive or negative charge
on it. A positively charged complex ion is called cationic
complex ion, while the negatively charged complex ion is
termed as anionic complex ion. For example,
Cationic complex ions : [Ag(NH3)2]+, [Cu(NH3)4]2+,
[Co(NH3)6]3+, etc.
Anionic complex ions .'[Fe(CN)6]4-, [Cu(Cl)4]2-,
[Ag(CN)2]- etc.
While writing the formula of a complex ion, the
ligands are usually written inside the parenthesis, and the
entire complex ion in a square bracket. The net charge
present on the complex ion is written at the right hand top
corner of the square bracket.
4. Coordination sphere and ionic sphere : The part
consisting of the- central metal atom and ligands directly
attached to it (enclosed in square brackets) is called the
coordination sphere of the complex compound, while
the part which gets ionised in solution (written outside
square brackets) is called the ionic sphere of the complex
compound. For example, the complex, [Cu(NH3)4jSO4
ionises in solution as
[Cu(NH3)4]SO4 [Cti(NH3)4]2+ + SO2-
Complex compound (coordination sphere) (ionic sphere)
-X 2+
Obviously, the part [Cu(NH3)4] constitutes the
coordination sphere while SO2- the ionic sphere of this
complex.
5. Coordination polyhedron : The spatial arrangement
of the ligands directly attached to the central atom or
ion constitute a polyhedron about the central atom. This
polyhedron is termed as coordination polyhedron. The
coordination polyhedron may be tetrahedral, square
planar, octahedral, trigonal bipyramidal, etc., in shape.
6. Cationic, anionic and neutral complexes: Coordination
compounds or complexes may be of following three types.
(i) Cationic complexes : The complexes in which the
complex ions carry a net positive charge are called cationic
complexes. For example, [Fe(H2O)6]Cl3, [Co(NH3)6]C13,
[Ni(NH3)6]Cl2, etc. The complex ions present in these
complexes carry a net positive charge as is clear from the
following.
[Fe(H2O)6]Cl3 [Fe(H2O)6]3+ + 3CF
[Co(NH3)6]C13 [Co(NH3)6]3++ 3C1
Nootan ISC Chemistry-XII
(ii) Anionic complexes : The complexes in which the
complex ions carry a net negative charge are called anionic
complexes. For example, K4[Fe(CN)6], K[Ag(CN)2],
K2[HgI4], etc. These complexes possess anionic complex
ions as is clear from the following.
K4[Fe(CN)6] 4K++ [Fe(CN)6]4“
K2[HgI4] 2K++[HgI4]2"
(iii) Neutral complexes : The complexes which carry
no net charge are called neutral complexes. For example,
[Ni(CO)4], [Pt(NH3)2Cl2], etc.
7. Coordination number: The maximum number of ligands
which can be coordinated to a central metal atom or ion is
known as the coordination number of that central atom
or ion. For example, in K4[Fe(CN)6], six CN- ligands are
9i
coordinated to central Fe ion. Therefore, its coordination
number is six. Similarly, in [Cu(NH3)4]SO4, the coordination
number of Cu is four. Coordination numbers of metals vary
from 2 to 10 but the most common coordination numbers are
4 and 6. The coordination number of a metal ion depends
mainly upon its nature, its oxidation state and on the nature
of ligands surrounding it. However, coordination number
may be influenced by temperature, pressure and nature of
solvent. A particular metal may exhibit different coordination
numbers in different complexes. For example, platinum has
coordination number 4 in [PtCl4]2-, while coordination
number 6 in complex ion [PtClg]4-.
The geometry of a complex depends upon the
coordination number of its central metal atom. Central
metals with coordination number 6 usually form octahedral
complexes, while those with coordination number 4 usually
form tetrahedral or square planar complexes.
8. Charge number of a complex ion : The net charge
carried by a complex ion is called its charge number. It
is equal to the algebraic sum of the charges carried by
central ion and the ligands attached to it. For example, the
charge number of [Fe(CN)6]4- is - 4. It may be calculated
as shown below :
Charge number of
[Fe(CN)6]4 = (charge on Fe2+) + (6 x charge on CN- ion)
= (+2) + 6 x (-1) = - 4.
9. Oxidation number or oxidation state of the central metal
atom : The number which represent the electrical charge which
the central atom actually has or appears to have when combined
with other atoms or groups of atoms is called the oxidation
number or the oxidation state of the central metal atom.
For example, the oxidation state of iron in the complex,
K4[Fe(CN)6] is +2.
The oxidation number or oxidation state of the central
metal atom may be calculated according to the common
rules used for the purpose which we have already studied
in class XI. Following examples illustrate the procedure.
Coordination Compounds ___________ ________________________________ 485
(i) Oxidation number of Cu in [Cu(NH3)4] SO4 : [B] Classification on the Basis of the Number of
Suppose the oxidation number of Cu in this complex is x.
Donor Atoms
Since it is a neutral molecule, the sum of oxidation numbers The mode of attachment of a ligand to the central metal
of all the species in it should be equal to zero. Hence, atom or ion is decided by the number of donor atoms present
x + 4x(0)-2 = 0 or, x = + 2. in it. The number of such ligating groups (donor atoms) is
Therefore, the oxidation number of Cu in this complex called denticity of the ligand. Depending upon the number
is+ 2. of donor atoms, ligands can be classified as follows.
o
(ii) Oxidation number of Fe in [Fe(CN)6] ion : 1. Unidentate ligands : The ligands which possess only
Suppose the oxidation number of iron is x. The sum of one donor atom and can form only one coordinate bond to the
oxidation numbers of all the species present in it should be central metal atom or ion are called unidentate ligands or
equal to the charge present on the ion. Hence, monodentate ligands. Such ligands can attach themselves
x + 6 x (-1) = - 3 or, x = + 3. to the central atom through one point only. They may be
neutral as well as anionic. Some important monodentate
Thus, the oxidation number of Fe in this complex ion
ligands, their names and donor atoms present in them are
is +3.
listed in Table 9.1.
(iii) Oxidation number of Au in H[AuC14] : If the Table 9.1 Some Important Unidentate Ligands
oxidation number of gold in this complex is x, we have
Donor Donor
+1 +x + 4 x (-1) = 0 or, x = + 3. Ligand Name Ligand Name
atom atom
Thus, the oxidation number of Au in this complex is
H2O aqua 0 r iodido I
+ 3.
(iv) Oxidation number of Ni in [Ni(CO)4] : If the nh3 ammine N CN” cyanido C or N
oxidation number of nickel in this complex is x, we have CO v. carbonyl 0 OH” hydroxo 0
x + 4 x (0) = 0 or, x - 0.
NO nitrosyl N no2 nitro N
Thus, the oxidation number of Ni in this complex is 0.
10. Homoleptic and heteroleptic complexes : The C5H5N pyridine N —ONO” nitrito 0
complexes in which the central metal atom or ion is linked (py)
to only one kind of donor groups (ligands) are called F" fluorido F CH3COO” acetato 0
homoleptic complexes, e.g, [Fe(CN)6]4~, [Co(NH3)6]3+, cr chlorido Cl SCN” thiocyanato S
etc. Complexes in which the central metal is bound to more Br” bromido Br NCS” isothiocyan ato N
than one kind of donor groups are termed as heteroleptic NH2" imido N NH2 amido N
complexes, e.g, [Co(NH3)4Cl2]+ [Co(NH3)5(SO4)]+, etc.

9.1.3 Classification of Ligands 2. Didentate ligands : The ligands which possess two
donor atoms and can form two coordinate bonds with the
As discussed /earlier, ligands are those atoms or
central metal atom or ion are called didentate ligands.
groups of atoms which have a tendency to donate a lone
Such ligands can get attached to the central metal atom or
pair of electrons to the central metal atom or ion. The
ion through two points. Some important didenate ligands
ligands can be classified as follows.
are listed in Table 9.2.
|A| Classification on the Basis of Charge Table 9.2 Some Important Didentate Ligands
Depending upon the nature of charge (electrical) Ligand Name Donor atoms
Present, ligands can be classified as follows. oxalato (ox) O and O
COO2”
1. Neutral ligands : Such ligands possess no electrical
charge present on them. They are usually molecular
COO
species having one or more lone pairs of electrons. For
NH2CH2COO" glycino (gly) N and O
example, H2OI (aqua), NH3 (ammine), CO (carbonyl),
ch2nh2 ethylenediamine or N and N
h'O (nitrosyl), C5H5N (pyridine, py), etc.
ethane-1, 2-diamine
2. Anionic ligands : Such ligands carry negative charge (en)
ch2nh2
them. These are anionic species containing one or
■"ore lone pairs of electrons. For example, F- (fluorido), CH3 — C = N — OH dimethylglyoximato N and O
-i (chlorido), Br” (bromido), I” (iodido), CN” (cyanido), (DMG)
(hydroxo), CH3COO” (acetato), etc. CH3 — C = N — 0“
3. Cationic ligands : Such ligands carry positive charge 2, 2'-dipyridyl N and N
(pUo)
occur very rarely in complexes. For example, NO+ (dipy)
(’litrosylium), NH2NH3 (hydrazinium), etc. •• ••
 486 Nootan ISC Chemistry-XII
3. Tridentate ligands : The ligands which possess three Some common chelating ligands are ethylene-diamine
donor atoms and can form three coordinate bonds with the (en), oxalato (ox), diethylenetriamine (dien), EDTA, etc.
central metal atom or ion are called tridentate ligands. For For example, the complexes formed by the bidendate
example, ligand ethylenediamine (en) with Cu (II) and Pt (II) ions
are chelates. These are shown below.
NH2 —CH2 —CH2 —NH—CH2 —CH2 —nh2
Diethylenetriamine (dien) H2C—H2N NH2— ch2
I Cu |
ooc—ch2— ch —cop/ H2C—H2N NH2 — CH2
nh2 or, [Cu(en)2]2+
Aspartate ion (asp)
H2C—H2N NH2 —CH2'
4. Tetradentate ligands : The ligands which possess I Pt I
four donor atoms are called tetradentate ligands. h2c—h2n r nh2-ch2
For example,
or, [Pt(en)2]2+
NH2 —CH2 —CH2 —NH—CH2 —CH2 — NH—
Chelating ligands stabilise a complex. This is why
chelates are more stable than the ordinary complexes
CH2— ch2— nh2
Triethylenetetramine (trien)
containing monodentate ligands which are unable to form
chelates.
5. Pentadentate ligands : The ligands which contain five
Chelates find a wide range of applications in the
donor atoms are called pentadentate ligands. For example,
laboratory as well as in industry. They are used for
.. /CH2COO“ the detection and estimation of several ions such as
~OOCCH2 —NH—CH2 —CH2 —N < nickel (II), copper (II), magnesium (II), etc., in qualitative
’• xCH2COO“
and quantitative analysis. They are also used for softening
Ethylenediaminetriacetato of hard water and in the separation of lanthanoids and
6. Hexadentate ligands : The ligands which contain six actinoids.
donor atoms are termed as hexadentate ligands. 9.1.5 Werner's Theory of Coordination
For example,
Compounds
OOCCH2 <b .. ch2coo~
Alfred Werner (1892) prepared and isolated several
)N—CH2— CH2— N<
~oocch2z xCH2COO~ complex compounds by the action of ammonia on cobalt
chloride. He characterised these compounds as follows.
Ethylenediaminetetraacetato (EDTA)
Compound Colour Name according to colour
7. Bridging ligands : The monodentate ligands which can
simultaneously attach themselves to more than one metal ion CoCl3 ■ 6NH3 Yellow Luteo complex
are called bridging ligands. The ligands OH-, NH2, NO2, C0CI3 ■ 5NH3 Purple Purpureo complex
Cl-, CO, etc., act as bridging ligands. C0CI3 ■ 4NH3 Green Praseo complex
C0CI3 • 4NH3 Violet Video complex
9.1.4 Chelating Ligands and Chelates
The ligands containing two or more donor atoms are He studied the properties of these compounds in detail.
usually referred to as polydentate ligands. These ligands In order to explain the properties of these compounds, he
may contain donor atoms positioned in such a way that proposed a theory commonly known as Werner’s theory of
they may form a five or six membered ring with the metal coordination compounds. This theory is briefly described
below.
ion. Such ligands are termed as chelating ligands and the
Postulates of Werner’s theory : The main postulates of
rings thus formed are called chelates. They may be defined
Werner’s theory are as follows :
as follows.
(i) The central metal atom or ion present in a complex
When a polydentate ligand attaches itself to a central exhibits two types of valencies-primary valency and
ion through two or more donor atoms in such a way that it secondary valency.
forms a five or six membered ring with the central ion, the (a) Primary valency : This type of valency (linkage)
is ionisable and corresponds to the oxidation state
ligand is called chelating ligand and the ring thus formed is
of the central metal ion. It is always satisfied by
called a chelate.
a negative ion. The primary valencies are shown
Coordination Compounds ___________________________________________ ' 487 |

by dotted lines. The ions attached to the central of cobalt is six, it must have six secondary valencies.
metal ion through primary valencies can ionise In order to satisfy all the six secondary valencies,
in solution. one Cl atom (already attached by a primary valency) must
(b) Secondary valency : This type of valency also be linked by a secondary valency and the complex
(linkage) is non-ionisable and corresponds to the should have the structure as shown in Fig. 9.2. The Cl
coordination number of the central metal atom or atom linked by both primary and secondary valencies does
ion. Every central metal atom or ion has a fixed not ionise in the solution. Therefore, this complex should
number of secondary valencies (this number, ionise in the solution as follows :
infact, refers to the coordination number of the
CoC13-5NH3 ----- > [CoCi • 5NH3]2+ + 2CF
central metal ion). The secondary valencies are
satisfied either by negative ions or by neutral
molecules. They are represented by thick lines
and the groups attached to the central metal ion
through them are unable to ionise in the solution.
(ii) The central metal atom or ion has a tendency to satisfy
all of its primary and secondary valencies. In order to
meet this requirement, the central metal atom or ion
may attach one or more negative ions through both
primary and secondary valencies. Thus, some of the
negative ions may play a dual role. Such ions do not Fig. 9.2 Werner’s structure of C0CI3 • 5NH3.
ionise in solution. This has been confirmed conductometrically. One
(iii) The secondary valencies are directional, i.e., they point mole of the complex is found to give two moles of CF ions
in definite directions in space. The primary valencies are and onexmole of [CoC1-5NH3]2+ ion.
non-directional. 3. C0CI3 4NH3 and C0CI3 3NH3 : Following the
Structures of Some Coordination Compounds on arguments as given above, the structures of these complexes
can be written as shown in Fig. 9.3.
the Basis of Werner's Theory
The structures of some complexes derived on the basis
of Werner’s theory are discussed below.
1. C0CI3 • 6NH3: In this complex, cobalt is in +3 oxidation
state. Therefore, its primary valency is 3. Experimentally, it
has been observed that one mole of the complex gives three
moles of CF ions in solution. Therefore, the three Cl atoms
(negative ions) present in it should be linked to the central
cobalt by primary valencies. The coordination number of
cobalt is six. Therefore, it must have six secondary valencies.
Obviously, the six NH3 molecules (neutral molecules) must
Fig. 9.3 Werner’s structure of (a) CoC13-4NH3 and
be attached to cobalt by these secondary valencies. Thus,
(b) CoC13-3NH3.
on the basis of Werner’s theory, the complex C0CI3 • 6NH3
should be represented as shown in Fig. 9.1. On the basis of the Werner’s structures of the above
mentioned complexes of cobalt, the ionisation behaviour of
these complexes can be summarised as given in Table 9.3.
Table 9.3. Ionisation Behaviour of Some Cobalt Complexes

Number
of Total
Complex Ionisation behaviour ionisable number
chlorine of ions
atoms
nh3
CoC13-6NH3
Fig. 9.1 Werner’s structure of C0CI3 • 6NH3. CoC13-6NH3 3 4
----- > [Co-6NH3]3+ + 3CF
2. C0CI3 5NH3 : The oxidation state of cobalt in
this complex is +3. Therefore, it should have three
CoCl3 • 5NH3
primary valencies and all the three Cl atoms should
CoC13-5NH3 ----- > [CoCi • 5NH3]2+ + 2CF 2 3
be linked to cobalt by these valencies. The remaining
five NH3 molecules should be attached to cobalt by
secondary valencies. Since the coordination number
 Nootan ISC Chemistry-XII

C0CI3 • 4NH3 ionisable atoms or groups out side the square brackets. If
CoC13-4NH3 1 2 ligands attached to the central metal atom or ions are of
—> [coci2- 4nh3]+ + cr different types, they are represented in the order-anionic
CoC13-3NH3 Does not ionise ligands, neutral ligands, cationic ligands. If there are several
- -
ligands of the same kind, they are listed alphabetically
Werner’s theory was the first attempt to explain the according to the first symbol of their formulae. Thus, the
nature of bonding in coordination compounds and the modem notation of a coordination compound is in the
theory successfully explained the ionisation behaviour of following form :
several complexes. However, the bonding in complexes is For example,
more complicated. Therefore, the theory was vindicated Werner’s Modern Werner’s Modern
and several advanced theories were given to explain the Formula Notation Formula Notation
nature of bonding in complexes. Some of these theories CoC13-6NH3 [Co(NH3)6]C13 CoC13-5NH3- [Co(H2O)
will be discussed later on in this unit. h2o (NH3)5]C13
Modern Notation for Representing Coordination CoC13-5NH3 [CoC1(NH3)5] CoSO4-5NH3-Br [Co(SO4)
Compounds Cl2 (NH3)5]Br
Now-a-days, coordination compounds are represented CoC13-4NH3 [CoCl2(NH3)4] PtClBrNH3py [PtBrCl(NH3)
Cl py]
by enclosing complex ions (central metal atom or ion and
unionisable groups, i.e., ligands) in square brackets with CoCl3 • 3NH3 [C0CI3 (NH3) 3]

REVIEW EXERCISES
9.1 What are coordination compounds and how do they 9.8 What is the oxidation state of platinum in the
differ from double salts? Explain with examples. complex, [Pt(NH3)2CI2]C12?
9.2 Explain the following terms with respect to [Ans. + 4]
coordination compounds: 9.9 What is the oxidation state of cobalt in the complex,
(i) Ligands [Co(NH3)4(H2O)Br] (NO3)2?
(ii) Coordination sphere [Ans. + 31
(iii) Coordination number. 9.10 What is the coordination number of Fe in the
9.3 What is the oxidation state of Ni in Ni(CO)4? complex, K3[Fe(C2O4)3]?
|Ans. 0] [Ans. six]
9.4 Calculate the oxidation number of the central metal 9.11 What is the coordination number of cobalt in
[Co(en)(H20)(Br)(Cl)2]?
atom (underlined) in each of the following complex
[Ans. six]
species:
9.12 What is meant by a hexadentate ligand? Give an
(i) K4[Fe(CN)6] (ii) [Fe(H2O)6]CI3 example.
9.13 What do you understand by chelating ligands and
(iii) [Co(NH3)6]' (iv) [Fe (C2O4)3]'
what are chelates? Give one example of each.
[Ans. (i) +2, (ii) +3, (iii) +3, (iv) + 3] 9.14 Give one example of each of the following :
9.5 In the complex ion [Co(NH3)3(H2O)2CI]+: (i) a neutral ligand
(a) identify the ligands' formulae and charge on each (ii) an anionic ligand
of them; (iii) a cationic complex ion
(b) write the geometry of the complex ion. (iv) an anionic complex.
[Ans. (a) (i) NH3, 0 (ii) H2O, 0 (iii) CP, - 1 9.15 Calculatethechargenumberofthefollowingcomplex
(b) octahedral] ions :
9.6 Define coordination number. Find the coordination (i) [Co(NH3)4Cl2l+ (ii) [Pt(NH3)2CI2].
number of the central metal atom in each of the |Ans. (i) + 1, (ii) 0]
following : 9.16 What is the coordination number of central metal
ion in [Fe (C2O4)3]3 ?
(i) [Co(NH3)5CI] Cl2 (ii) K2[FeCI4]
[Ans. (i) six, (ii) four] [Ans. six]
9.7 What is the oxidation state of Co in the complex, 9.17 Give an example of chelate complexes.
9.18 Why is ammonia molecule a good ligand?
[Co(NH3)2(N02)CI] [Au(CN)2]?
9.19 Name a ligand which is bidentate and give an
[Ans. + 3] example of the complex formed by this ligand.
Coordination Compounds 489

9.2 NOMENCLATURE OF COORDINATION COMPOUNDS

Coordination compounds are named according to cr chlorido OH" hydroxo
the IUPAC system of nomenclature suggested in 1957 and O2"
Br“ bromido oxo
later on modified in 1959. The Inorganic Nomenclature
r iodido SCN" thiocyanato
Committee of the International Union of Pure and Applied
Chemistry (IUPAC), further modified the system of CN" cyanido c2ot oxalato
nomenclature of coordination compounds in 1990. The
system was further modified in 2004. The procedure of the SO2" sulphato (O—O)2~ peroxo
IUPAC nomenclature of coordination compounds according
to the latest system is described below. so2-
CH3COO" acetato sulphito
9.2.1 Rules for Naming the
S2“ sulphido NH2 amido
Coordination Compounds
According to the latest IUPAC recommendations, N3 azido no3 nitrato
following rules are observed for naming the coordination
compounds. CO2" carbonato nitro
no2
1. Order of naming ions : In ionic complexes, the
positive ion (cation) is named first followed by the name of S2O2" thiosulphato ONO" nitrito
the negative ion (anion). The name is started with a small
letter and the complex part is written as a single word. The (c) Positive ligands occur very rarely in complexes.
These are named by putting a suffix -ium to the respective
names ofnon-ionic complexes are written as single words.
name of the group. For example,
For example, the complex K4[Fe(CN)g] ionises as . t +
NO nitrosonium NH2 NH3 hydrazinium
K4[Fe(CN)6] ?=± 4K+ +[Fe(CN)6]4“
NO2 nitronium
Obviously, it is an anionic complex. Its positive part 3. Mode of attachment of an ambident ligand : Some
consists of K+ ions, while the negative part [Fe(CN)6]4" monodentate ligands contain more than one donor atom
ion. Therefore, its IUPAC name consists of the name and can attach themselves to the central metal atom
of positive part (K+) followed by the name of negative through any of its donor atoms. Such ligands are called
part, i.e., [Fe(CN)6]4~. Similarly for the complex ambident ligands. In such a case, the name of the ligand
[Fe(H2O)6]Cl3, the name of the positive part, i.e., is written in the following two ways.
[Fe(H2O)6]3’’ will be written first and it will be followed by (i) The name of the ligand is followed by the symbol
of the atom through which it gets attached to the
the name of the negative part, i.e., Cl" ion. central metal atom. For example, the ligand SCN"
2. Nomenclature of ligands : Different types of ligands is an ambident ligand and can get attached through
are named as follows. S as well as through N. *Therefore, ••
it is named as
(a) Neutral ligands are named as molecules. thiocyanato-S or thiocyanato-N depending upon
For example, its mode of linkage.
(ii) The different modes of attachment of an ambident
CO Carbonyl ligand are also expressed by giving different names
CS thiocarbonyl to the ligand for different modes of attachment.
NO nitrosyl
For example, the ligand NO2 can attach either
NH2CH2CH2NH2 ethylenediamine (en)
C5H5N pyridine through N (as -NO2 ) or through O (as — ONO").
(CH3)3P triphenylphosphine
It is designated as nitro and nitrito depending
Water (H2O) and ammonia (NH3), when used as upon its mode of attachment through N and O
ligands, are assigned special names. The ligand H2O is respectively.
named as aqua and the ligand NH3 is named as ammine. 4. Number of ligands :
(b) Negative ligands are named by putting a suffix -o (i) When two or more ligands of the same type occur
to the respective name of the group. For example, in the same complex, the prefixes di, tri, tetra,
penta, hexa, etc., are used to indicate their number.
• Earlier the ligand H20 was named as aquo. For example, in the complex [Fe (H2O)6]Cl3,
•• According to IUPAC recommendations (2004), the anionic ligands
there are six H2O ligands. Therefore, the suffix
should end with -Ido or 0. Thus, chloro would become chlorido.
 490
hexa will be added to the name of the ligand, i.e.,
aqua and the ligands present will be expressed as
hexaaqua. Similarly, the two NH3 ligands present
in the complex, [Ag(NH3)2]Cl will be named as
diammine.
(ii) When the name of a polydentate ligand includes
a numerical prefix such as di, tri, etc., (e.g.,
ethylenediamine, ethylenediaminetetraacetate,
etc.), the suffixes bis, tris, tetrakis,pentakis, hexakis,
etc., are used to describe two, three, four, five, six,
etc., ligands respectively. In such a case, the name
of the ligand is written within brackets without
any hyphens. For example, the complex [Cu(en)2]
SO4 contains two ethylenediamine ligands. In
this case, the ligands present are described as bis
(ethylenediamine).
(iii) The prefixes bis, tris, etc., are also used to indicate
the number of some monodentate ligands such
as methylamine because the use of prefixes, di,
tri, etc., in such a case may create unnecessary
confusion.
5. Order of naming ligands : When more than one type
of ligand are present in a complex, they are named in the
alphabetical order* regardless of the nature of charge
present on them. The names of all ligands are written as a
single word without any separation by hyphens. Following
examples illustrate the procedure.
(a) The ligands present in the complex, [Co(Cl)
(CN)(NO2)(NH3)3] will be named as
triamminechloridocyanidonitrito.
(b) The ligands present in the complex,
[Pt(NH3)4(NO2)(Cl)]2+ will be named as
tetraamminechloridonitrito.
(c) The ligands present in the complex, [Cr(H2O)5Cl]
Cl2 will be named as pentaaquachlorido.
It is to be noted that the prefixes di, tri, etc., are
not taken into account while arranging the ligands in
alphabetical order.
6. Nomenclature of bridging ligands : A bridging ligand
is indicated by adding the prefix p before the name of the
ligand. The name of the ligand is separated from p by a
hyphen. Bridging ligands are also written in the alphabetical followed by its oxidation state in Roman numeral enclosed in
order with the names of other ligands present in the complex. brackets. For example,
If the complex contains two or more similar bridging ligands,
the prefixes di, tri, etc., are used to indicate their numbers.
For example, the complex,
z0H\
(H2O)4Fe( )Fe(H2O)4 (SO4)2,
XOHZ
contains two OH bridging and eight H2O non-bridging
ligands. This complex will be named as tetraaquairon
(III)-p-dihydroxo tetraaquairon (III) sulphate.
* Earlier, the different types of ligands were named in the order: (i)
negative, (ii) neutral and (iii) positive.
Nootan ISC Chemistry-XII
7. Nomenclature of central metal ion : The procedure of
naming the central metal ion depends upon the nature of
the complex.
(i) Cationic and netural complexes : When the
complex is cationic or netural, the central metal atom
or ion is described by its common name as used in other
compounds. The name of the metal atom or ion is followed
by its oxidation state (in the complex). The oxidation state
of the metal atom or ion is written in Roman numeral and
is enclosed within brackets.
For example, in the complex, [Ag(NH3)2]Cl, the
central metal ion is Ag+ and its oxidation state is +1. It will
be named as silver (I). Similarly, the metal ion present in
the complex, [Fe(H2O)6]Cl3, will be named as iron (III) as
its oxidation state in the complex is + 3.
(ii) Anionic complexes : When the complex is anionic,
the name of the central metal atom or ion ends with the
suffix ate and is followed by its oxidation state written in
Roman numeral and enclosed within brackets.
For example, the central metal ion present in the
complex, K4[Fe(CN)6], will be named as ferrate (II).
Similalry, the central metal ion present in the complex,
K[Ag(CN)2], will be named as argentate (I).
8. Nomenclature of complex ions : The nomenclature of
complex ions depends upon their nature.
(a) Cationic complex ions and neutral complex
species : Such complexes are named by writing the number
and names of ligands followed by the name of the central
metal atom or ion which is further followed by its oxidation
state in Roman numeral enclosed in brackets. For example,
[Cu(NH3)4]2+ tetraamminecopper (II) ion
[Fe(H2O)6]3+ hexaaquairon (III) ion
[CoCl2(en)2] dichloridobis (ethylenediamine)
cobalt (II).
(b) Anionic complex ions : Such species are named
by writing the number and names of ligands followed by the
name of the central metal ion ending with ate which is further
[Fe(CN)6] hexacyanidoferrate (III) ion
o_
[Hgl4] tetraiodidomercurate (II) ion
[AuC14]~ tetrachloridoaurate (III) ion.
9. Nomenclature of geometrical isomers: A large number
of complexes show geometrical isomerism and exist in cis
and trans forms. The cis and trans forms of a complex are
named by prefixing the name of the complex by the word
cis or trans as the case may be. The prefixes cis and trans
are separated from the name of the complex by hyphens.
For example,
Coordination Compounds 491

NHo------------ ;;C1 NH3------------;;C1 Common (Oxidation

/ X ■ / / ** X. ^ *** / Number
name of the state in Name of the
/ x:ptr"' / / X and name of
central metal Roman anion
ligands
nh3'-'--------- ?-ci Cl------------- -NH3 atom or ion numerals)

ds-diamminedichloridoplatinum (II) trans-diamminedichloridoplatinum (II) Following examples illustrate the procedure.

Cationic Complex IUPAC Name
10. Nomenclature of optical isomers : A large number
[Cu(NH3)4]SO4 tetraamminecopper (II)
of complexes also show optical isomerism and exist in
sulphate
enantiomeric forms. The dextro- and laevo- rotatory
[Ag(NH3)2]Cl diamminesilver (I)
optically active complexes are named by prefixing their
chloride
names either by d- and I- or by (+) and (-) respectively.
[Fe(H2O)6]SO4 hexaaquairon (II)
sulphate
[Fe(H2O)6]Cl3 hexaaquairon (III)
chloride
[Co(NH3)6]Cl3 hexaamminecobalt (III)
chloride
[Cr(Cl)(H2O)5]Cl2 pentaaquachloridochro-
mium (III) chloride
[Co (Cl) (NO2) (NH3)4] C1O4 tetraamminechloridoni-
trocobalt (III) perchlorate
[Co(en)3]Cl3 tris (ethylenediamine)
chromium (III) chloride
[Co(Cl)2(en)2]SO4 dichloridobis
(ethylenediamine) cobalt
d-tris (ethylenediamine) cobalt (III) ion (IV) sulphate
or (+)-tris (ethylenediamine) cobalt (III) ion [Co(Cl)(ONO)(en)2]Cl chloridobis
(ethylenediamine)
nitritocobalt (III) chloride
It is to be noted that the name of the anion present in
a cationic complex is not prefixed by the numerical prefixes
such as di, tri, etc., even when there are more than one
anion present in the complex.
2. Nomenclature of anionic complexes : The anionic
complexes are named by writing the name of the cation
present in the complex followed by the name of the complex
anion (as described earlier). Thus, following sequence is
observed while writing the name of an anionic complex.
Name of the (Oxidation
Number
Name of the central metal state in
and name of
Z-tris (ethylenediamine) cobalt (III) ion cation ion with Roman
or (-)-tris (ethylenediamine) cobalt (III) ion ligands
suffix ate numerals)

9.2.2 Nomenclature of Simple Following examples illustrate the procedure.

Mononuclear Complexes Anionic Complex IUPAC Name
The nomenclature of simple mononuclear (containing K[Ag(CN)2] potassium dicyanidoargentate (I)
only one acceptor metal ion) complexes depends upon H[AuC14] hydrogen tetrachloridoaurate
whether they are cationic or anionic. (HI)
1. Nomenclature of cationic complexes : The cationic K3[AgF4] potassium tetrafluoridoargentate
complexes are named by writing the name of the complex
(I)
cation (as described above) followed by the name of the
anion present in the complex. Thus, following sequence is K4[Fe(CN)6] potassium hexacyanidoferrate
observed while writing the name of a cationic complex. (ID
 492 Nootan ISC Chemistry-XII

K3[Fe(CN)6] potassium hexacyanidoferrate ligand by symbol p (mu) separated by hyphens. The symbol
(III) p is repeated before the name of each different kind of
bridging ligand present in the complex. Following examples
K2[HgI4] potassium f etraiodidomercurate
illustrate the procedure of nomenclature of the bridged
(ID polynuclear complexes.
K3[A1(C2O4)3] potassium trioxalatoaluminate
(III) z0H\
K3[Co(CN)5NO] potassium (H2O)4Fe< )Fe(H2O)4 (SO4)2
XOHZ
pentacyanidonitrosylcobaltate
(ID tetraaquairon (Ill)-p-dihydroxotetraaquairon (III) sulphate.
K[PtCl3(NH3)] potassium
amminetrichloridoplatinate (II) NH2
(NH3)4Co( XCo(NH3)4 (NO3)4
Dextro K3[Ir(C2O4)3] potassium-d-trioxalatoiridate xNO2z
(HI)
ammonium diamminetetra tetraamminecobalt (Ill)-p-amido-p-nitrotetraamminecobalt (III)
NH4[Cr(NCS)4
nitrate
(NH3)2] (thiocyanato - N) chromate (III)
Na2[Ni(EDTA)] sodium ethylenediaminetetraac- /NH\
etatonickelate (II) (en)2Co<f yCo(en)2
It is to be noted that the name of the cation present in an XOHZ
anionic complex is not prefixed by numerical prefixes such as bis (ethylenediamine)
di, tri, etc., even when there are more than one cation present cobalt(III)-p- hydroxo-p- imido-
bis (ethylenediamine) cobalt (III) ion
in the complex.
9.2.3 Nomenclature of Complexes z°H\
(C2O4)2Crv /Cr(C2O4)2
Containing Complex Cationic and XOHZ
Complex Anionic Species dioxalatochromium (III) -p-dihydroxodioxalatochromium (III) ion
The coordination compounds containing complex (C6H5)3P Cl Cl
cations and complex anions are also quite common. Such
coordination compounds are named by writing the name /pd\
of the complex cation followed by the name of the complex Cl Cl 'P(C6H5)3
anion. The complex cation and complex anion are named chloridotriphenylphosphinepalladium(II)-p-di
exactly in the same way as described earlier. Following chloridochloridotriphenylphosphinepalladium (II).
examples illustrate the procedure.
9.2.5 Writing Formula of a Simple
[Cr(NH3)6] [Co(CNJ6] hexaamminechromium (III)
hexacyanidocobaltate (III) Mononuclear Complex from its
[PtCl2(NH3)4] [PtCl4] tetraamminedichloridoplati- IUPAC Name
num (IV) tetrachloridoplati- The formula of a simple mononuclear complex can
nate (II) easily be written if its IUPAC name is known. The rules
involved and the procedure are as follows.
[CoC12(NH3)4]3 [Cr(CN)6] tetraamminedichloridocobalt (i) Identify the central metal and the ligands attached
(III) hexacyanidochromate to it. Write their formulae in the following order :
(III) [Metal atom; anionic, neutral, cationic ligands]
[Pt(py)4] [PtCl4] tetrapyridineplatinum (II) This constitutes the coordination sphere (complex
tetrachloridoplatinate (II) species) of the given complex. Enclose it in square
[Co(NH3)6] [CdCl5] hexaamminecobalt (III) brackets.
pentachloridocadmate (II) (ii) Calculate the charge on the complex species as
follows :
9.2.4 Nomenclature of Bridged Charge on a complex species = Oxidation state of the
Polynuclear Complexes central metal atom/ion + total charge on the ligands
attached.
The complexes having two or more acceptor metal
atoms are called polynuclear complexes. In such complexes, It is to be noted that the oxidation state of a
two or more acceptor atoms are bridged together through central metal atom/ion is always positive in a
certain ligands called bridging ligands. As mentioned earlier, complex. Consider it while carrying out the above
a bridging ligand is represented by prefixing the name of the calculation.
Coordination Compounds
(iii) If the charge calculated as above on the given
complex species is positive, the complex under
consideration is a cationic complex and would
contain anions in the ionic sphere. On the other
hand, if the charge is negative, it is an anionic
complex and would contain cations in the ionic
sphere.
(iv) The number of cations or anions present in the
ionic sphere of the given complex can be calculated
by multiplying the formula of the cation or anion
(mentioned in the name) by a suitable factor in
such a way that the total charge of the ionic sphere
becomes equal to that of the coordination sphere.
(v) In case of a cationic complex, write the ionic
sphere immediately after the coordination sphere;
while in case of an anionic complex, write the
ionic sphere immediately before the coordination
sphere. This will give the structure of the given
simple mononuclear complex. Following examples
illustrate the procedure.
Example 9.1 Give the chemical formula of potassium
hexacyanidoferrate (II).
Ans. As the name hexacyanidoferrate (II) implies, the
___________________________________________ 493
central metal in this complex is iron (Fe) and it is attached
to six cyanide CN- ligands. The oxidation state of iron is +2.
Charge on the complex species = + 2 + 6 x (-1) = -4.
Thus, the complex species should be represented as
[Fe(CN)6]4~. Further, the ionic sphere contains potassium
(K+) ions. In order to balance the charge, there should be
four K+ ions in the ionic sphere. Hence, the given complex
should have the formula K4[Fe(CN)6].
Example 9.2 Give the chemical formula of the compound
nitropentaamminecobalt (III) nitrate.
Ans. The name nitropentaamminecobalt (III) implies that
the given complex contains cobalt in the +3 oxidation state
and it is attached to one nitro and five NH3 ligands.
.'. Charge on the complex species
= +3 + (-1) + 5 x (0) = +2
Thus, the complex species should be represented as
9i
[Co(NOH2)(NH3)5] . Further, the ionic sphere contains
NO3 ions. In order to balance the charge, there should be
two NO3 ions. Hence, the given complex should have the
formula [Co(NO2)(NH3)5] (NO3)2.

REVIEW EXERCISES
9.20 Name the following complex ions in IUPAC system : [Ans. (i) potassium trioxalatoaluminate (III)
(i) [Co(CN)6]3~ (ii) pentaamminechloridocobalt (III) chloride
(ii) [Hgl4]2- (iii) potassium hexacyanidoferrate'(III) (iv) sodium
(iii) [Fe(H2O)6]3+ hexa nitrocobaltate (III)
(iv) [Cu(NH3)4]2+ (v) tris (ethylenediamine) chromium (III) chloride
(v) [CoCI(en)2NH3]2+ (vi) triamminetrichloridoplatinum
(vi) [CoCI2(NH3)4]+ (IV) chloride (vii) tris (ethylenediamine) cobalt
(vii) [Co,j(ONO) (NH3)5]2+ (III) hexacyanidochromate (III)
[Ans. (i) hexacyanidocobaltate (III) ion (viii) sodium ethylenediaminetetraacetatochromate
(ii) tetraiodidomercurate (II) ion (iii) hexaaquairon (II) (ix) pentaamminenitrocobalt
(III) ion (iv) tetraamminecopper (II) ion (III) chloride (x) Ammonium dramminetetra
(v) amminechloridobis (ethylenediamine) cobalt (III) (thiocyanato-N) chromate (III)
ion (vi) tetraamminedichloridocobalt (III) ion (xi) tetraamminediaquacopper (II) sulphate (xii)
(vii) pentaamminenitritocobalt (III) ion] tetrapyridineplatinum (II) tetrachloridoplatinate (II)
9.21 Give the IUPAC names of the following coordination (xiii) pentaamminenitritocobalt (III) chloride
compounds : (xiv) sodium hexafluoridoaluminate (III)]
(i) K3[AI(C2O4)3] 9.22 Give the chemical formula for each of the following
(ii) [CoCl(NH3)5]CI2
compounds:
(iii) K3[Fe(CN)6]
(i) copper (II) hexacyanidoferrate (II)
(iv) Na3[Co(NQ2)6]
(ii) potassium hexacyanidocobaltate (III)
(v) [Cr(en)3] Cl3
(iii) hexaammineplatinum (IV) chloride
(vi) [PtCl3(NH3)3] Cl
(vii) [Co(en)3][Cr(CN)6] (iv) potassium hexacyanidoferrate (III)
(viii) Na2[Cr(EDTA)] (v) pentaamminenitrocobalt (III) chloride
(ix) [Co(N02)(NH3)5] Cl2 (vi) tetrachloridocuprate (II) ion
(x) NH4[Cr(NH3)2 (NCS)4] (vii) chloridobis (ethylenediamine) nitrocobalt (III)
(xi) [Cu(H2O)2(NH3)4] SO4 ion
(xii) [Pt (py)4] [PtCI4] (viii) hexaaquamanganese (II) ion
(xiii) [Co(ONO)(NH3)5] Cl2 (ix) potassium hexachloridoplatinate (IV)
(xiv) Na3[A!F6] (x) triamminebromidonitrocobalt (II)
 494
[Ans. (i) Cu2[Fe(CN)6] (ii) K3[Co(CN)6]
(iii) [Pt(NH3)6] Cl4 (iv) K3[Fe(CN)6]
(v) [Co (NH3)5 (NO2)1 Cl2 (vi) [CuCI4]2-
(vii) [CoCI(N02) (en)2]+ (viii) [Mn(H2O)6]2+
(ix) K2[PtCI6] (x) [CoBr(NO2)(NH3)3]
9.23 Write the names of the following complexes using
IUPAC norms :
(i) [Cu(NH3)4] SO4
(ii) [Pt(NH3)2CI2]
(iii) [Ag(NH3)2CI]
(iv) Na3[AlF6]
[Ans. (i) tetraamminecopper (II) sulphate
(ii) diamminedichloridoplatinum (II)
(iii) diamminechloridoargentate (I) (iv) sodium
hexafluoridoaluminate (III)]
9.24 Write the IUPAC names of the complexes
[CoBr(NH3)5]S04 and [Co(SO4)(NH3)5]Br and give a
simple test to distinguish them.
[Ans. pentaamminebromidocobalt (III) sulphate,
pentaamminesulphatocobalt (III) bromide; the
former gives a white precipitate with BaCI2 while
the latter does not]
9.3 ISOMERISM IN COORDINATION COMPOUNDS
The phenomenon in which two or more substances
having the same molecular formula possess either different
chemical structures or different spatial arrangements of
atoms or groups is called isomerism and such substances are
called isomers.
Isomerism is quite common in coordination compounds.
They exhibit both types of isomerism, i.e., structural
isomerism as well as stereoisomerism. The structural
isomerism comes into existence due to their different
ionisation behaviour, difference in the position of ligands and
due to the different modes of linkage of ligands. On the other
hand, the stereoisomerism originates due to the different
stereochemical disposition of ligands around the central
metal atom or ion. Coordination compounds may show both
types of stereoisomerism, i.e., geometrical as well as optical
isomerism.
Various types of isomerism shown by complex
compounds is described below.
9.3.1 Structural Isomerism
In structural isomerism, two or more complex
compounds having the same molecular formula possess
different structural arrangements. Structural isomerism
shown by coordination compounds may be of following
types.
1. Ionisation isomerism : When coordination compounds
having the same molecular formula show a difference in their
Nootan ISC Chemistry-XII
9.25 Write the chemical formulae of the following
complexes :
(i) Hexaammineplatinum (IV) chloride
(ii) Tetraamminedichloridocobalt (III) chloride
lAns. (i) |Pt(NH3)6]CI4 (ii) [Co(NH3)4CI2]CI]
9.26 Write IUPAC name of the complex Na3[Cr(OH)2F4].
[Ans. sodium tetrafluoridodihydroxochromate (III)]
9.27 Name the following complex using IUPAC norms :
[Co (en)2 (ONO) Cl] Cl.
[Ans. chloridobis (ethylene diamine) nitritocobalt
(III) chloride]
9.28 A coordination compound has the formula
CoCI3 ■ 4NH3. It does not liberate ammonia but
forms a precipitate with AgNO3. Write the structure
and IUPAC name of the complex compound.
[Ans. [Co(NH3)4CI2]CI,
tetraamminedichloridocobalt (III) chloride]
9.29 Give the IUPAC name of [PtCI(NH2CH3)(NH3)2]CI.
[Ans. diamminechlorido(methylamine)platinum (II)
chloride]
9.30 Write the formula of the following complexes:
(i) Hexaammineplatinum chloride
(ii) Dichloridotetraammine cobalt ion.
[Ans. (i) [Pt(NH3)6]Cl4, (ii) [Co(NH3)4CI2]+]
ionisation behaviour and furnish different types of ions in
solution, the phenomenon is called ionisation isomerism.
Ionisation isomerism comes into existence due to
an exchange of groups between coordination and ionic
spheres. For example, two distinct compounds having the
formula Co(NH3)5(Br)(SO4) are as follows :
[CoBr (NH3)5]SO4
pentaamminebromidocobalt (III) sulphate
(red-violet)
and
[Co (SO4) (NH3)5] Br
pentaamminesulphatocobalt (Ill)bromide
(red)
The ionisation behaviour of these complexes is quite
different. They ionise in solution as given below.
[CoBr(NH3)5]SO4 ----- > [CoBr(NH3)5]2+ + SO4"
[Co(SO4)(NH3)5]Br ----- > [Co(SO4)(NH3)5]+ + Br“
The complex [CoBr(NH3)5]SO4 is red violet and
its aqueous solution gives a white precipitate of BaSO4
with BaCl2, thus confirming the presence of SO2-
ions in the solution. On the other hand, the complex
[Co(SO4) (NH3)5] Br is red in colour and its aqueous solution
gives a light yellow precipitate of AgBr with AgNO3, thus
confirming the presence of Br- ions in its solution.
Some other pairs showing this type of isomerism are :
(i) [PtCl2(NH3)4]Br2 and [PtBr2(NH3)4]Cl2
Coordination Compounds 495
(ii) [CoC12(NH3)4]NO2 and [CoC1(NO2)(NH3)4]C1 4. Coordination isomerism : This type of isomerism
(iii) [Pt(OH)2(NH3)4]SO4 and [Pt(SO4)(NH3)4] is shown by the complexes in which both positive and
(OH)2. negative parts are complex species. The isomerism arises
2. Hydrate isomerism : The water molecules can act due to the interchange of ligands between the coordination
spheres of positive and negative parts. Some pairs showing
both as ligands as well as simple molecules of water of
this type of isomerism are given below.
crystallisation. When two complexes differ in this aspect, they
[Co(NH3)6] [Cr(C2O4)3] and [Co(C2O4)3] [Cr(NH3)6]
exhibit hydrate isomerism. For example, with the formula
[Co(NH3)6] [Cr(CN)6] and [Co(CN)6] [Cr(NH3)6]
CrCl3 • 6H2O, following three isomers are known to exist. [Cu(NH3)4] [PtCl4] and [Pt(NH3)4] [CuCl4]
[Cr(H2O)s] Cl3 hexaaquachromium (III) In all these cases, the ligands have been changed
chloride (violet) within the coordination spheres. For example, in the last
[Cr(H2O)5Cl] C12.H2O pentaaquachloridochromium case, the first complex has cation [Cu(NH3)4]2+ and anion
(III) chloride monohydrate [PtCl4]2~. Its coordination isomer has cation [Pt(NH3)4]2+
(blue green) and anion [CuCl4]2-. Thus, the ligands coordinated to Cu
[Cr(H2O)4Cl2] C1.2H2O tetraaquadichloridochromium and Pt have been changed.
(III) chloride dihydrate (dark 5. Ligand isomerism: This type of isomerism arises when
green) the ligand present in the complex can exist in more than one
These isomers differ from each other in number
isomeric form. For example, the ligand diaminopropane
of water molecules coordinated to central chromium
can exist both as 1, 2-diaminopropane as well as 1,
atom. They possess different colours and may further be
3-diaminopropane.
differentiated by conductivity measurements.
ch2 — CH — ch3 CH2 — CH2 — CH2
Some other complexes showing hydrate isomerism
are nh2 nh2 nh2 nh2
(i) [CoC1(H2O)(NH3)4] Cl2 and [CoC12(NH3)4]
1, 2-diaminopropane (pn) 1, 3-diaminopropane (tn)
Cl • H2O
(ii) [CrCl2(H2O)2(py)2] Cl and [CrCl3(H2O) When these ligands coordinate to a metal atom or ion,
(py)2] • H2O. ligand isomers are obtained. For example, complexes
3. Linkage or structural salt isomerism : This isomerism [Co(pn)2Cl2]+ and [Co(tn)2Cl2]+
arises when the ligands have two different atoms available are ligand isomers.
for coordinating with metal ion, i.e., ligands are ambident. 9.3.2 Stereoisomerism
In one isomer one donor atom of the ligand coordinates with
the central metal atom, while in the other isomer the second Coordinate bonds are directional in nature and
donor atom coordinates with the metal atom. For example, give rise to the phenomenon of stereoisomerism in
in NO2 ion, both N and 0 atoms can coordinate with the coordination compounds. In this type of isomerism, different
central metal atom. Thus, following pair of compounds atoms or groups of atoms occupy different spatial positions
exhibits linkage isomerism. around the central metal atom. The isomers thus obtained
2+ are called stereoisomers.
nh3 nh3
Stereoisomerism is very common in coordination
h3n 4< no2 h3n 4- ONO compounds and is studied extensively. Stereoisomerism is
Xco\
of two types : geometrical isomerism and optical isomerism.
h3n^ t nh3 T NH3 Both are exhibited by complex compounds. A brief account
of these isomerism is given below.
nh3 nh3
pentaamminenitrocobalt (III) ion pentaamminenitritocobalt (III) ion [A] Geometrical Isomerism
(yellow brown) (red)
Geometrical isomerism comes into existence by
Although both pentaamminenitrocobalt (III) and the different spatial arrangements of groups around the
pentaamminenitritocobalt (III) ions contain NO2 group, central metal atom. Similar groups may either be arranged
yet they differ in colour and behaviour towards acids. The on the same side or on opposite sides of the central metal
former is yellow brown in colour and is stable towards atom. This gives rise to two types of isomers called cis and
acids, while the latter is red and is easily decomposed by trans isomers. When similar groups are arranged on the
acids to give nitrous acid. same side of the central metal atom, we have cis isomer,
Similarly, coordination compounds containing SCN~ and when the similar groups are spatially placed on the
Sroup as ligand also show linkage isomerism. opposite sides, we have trans isomer.
For example, Geometrical isomerism is common in coordination
[Cr(SCN)(H2O)5]2+ and [Cr(NCS)(H2O)5]2+. compounds and depends upon the coordination number
 496
of the central metal atom and also upon the geometry of
the complex. Various cases of this type of isomerism are
discussed below.
1. Four Coordination Compounds
Complexes with coordination number four are either
tetrahedral or square planar in shape. Tetrahedral complexes
can not show geometrical isomerism because all the four
ligands lie at the same distance from central metal atom.
Therefore, no case is observed where a tetrahedral complex is
found to show this type of isomerism.
Geometrical isomerism is very common in square
planar complexes. However, all square planar complexes
can not exhibit geometrical isomerism. Square planar
complexes of the type Ma4, Ma3b and Mab3 are unable
to exist in cis and trans forms (where a and b represent
monodentate ligands). Geometrical isomerism is shown
only by the following types of complexes.
(i) Complexes of the type (Ma2b2)n± : Complexes of
the type (Ma2b2)n± can exist in CIS and trans forms. Cis
form is obtained when both the groups a and both the
groups b occupy neighbouring positions, while trans form
is obtained when similar groups occupy trans positions
around the central metal M.
For example, the cis and trans forms of complex
diamminedichloridoplatinum (II), [PtCl2 (NH3)2] are
shown in Fig. 9.4.
Cis-isomer Trans-isomer
Fig. 9.4 Cis and trans isomers of [PtCl2(NH3)2].
Another complex of this type is [Pt(NO2)2(NH3)2]. It
can also exist in cis and trans forms in the same way as
shown above.
(ii) Complexes of the type (Ma2bc)n± : In this case, cis
isomer is obtained when similar groups a are adjacent to
each other and the trans form is obtained when they are
opposite to each other.
For example, the cis and trans forms of complex
diamminebromidochloridoplatinum (II), [PtBrCl(NH3)2]
exist as shown in Fig. 9.5.
Fig. 9.5 Cis and trans forms of [PtBrCl(NH 3)2],
(iii) Complexes of the type (Mabcd)1* : When all the
four ligands are different, three geometrical isomers are
Nootan ISC Chemistry-XII
possible in square planar complexes. An example of this type of
complex is [PtBrCl(NH3) (Py)L It can exist in the following
three forms (Fig. 9.6).
Fig. 9.6 Three geometrical isomers of [PtBrCI(NH3)(Py)].
(iv) Complexes of the type [M(AB)2]n : In the complex
[M(AB)2]n±, M is the central metal atom, while AB is an
unsymmetrical bidentate ligand. An example of this type
of complex is [Pt (gly)2L where gly stands for glycino,
(NH2CH2COO~) ligand. The cis and trans forms of this
complex are shown in Fig. 9.7.
Fig. 9.7 Cis and trans forms of [Pt(gly)2].
2. Six Coordination Compounds
Complexes with coordination number six are
octahedral in shape. A regular octahedron contains eight
faces and six equivalent vertices. In an octahedral complex,
the metal is placed at the centre and six ligands occupy their
positions at the vertices. Octahedral complexes of the type
Ma& Ma5b and Mab5 do not show geometrical isomerism
because in these complexes different spatial arrangements of
ligands are not possible. Geometrical isomerism in all other
types of octahedral complexes is very common. Some of
the important types of octahedral complexes showing
geometrical isomerism are as follows.
_ (I) Complexes of the type [/lfe4/f2],W:: In these complexes
four monodentate ligands a and two monodentate ligands
b are octahedrally attached to the central metal atom M.
Cis-isomer is obtained when ligands b occupy adjacent (1,
2) positions, while trans-isomer is obtained when ligands b
are opposite to each other, i.e., they occupy 1, 6 positions.
An example of this type of complex is [CoCl2(NH3)4]+.
The cis and trans forms of this complex cation are shown in
Fig. 9.8. In the cis-isomer, the two CF are at two adjacent
positions (any) and hence it is designated as cis isomer. In
trans isomer, the two CF are in opposite positions (any)
and therefore it is designated as trans isomer.
Coordination Compounds
Fig. 9.8 Cis and trans isomers of [CoC12(NH3)4]+.
(ii) Complexes of the type [Ma^]^ : An important
example of this type of complexes is [CrCl3(NH3)3]. Its cis
and trans forms are shown in Fig. 9.9.
In the cis-isomer, the three CF are on one triangular
face and the three NH3 molecules are placed on the opposite
triangular face. This isomer is designated as facial (fac)
isomer. In trans-isomer, CF are placed on the edges of
the octahedron, while NH3 molecules are present on the
opposite edges. This isomer is termed as meridonal (mer) or
peripheral isomer. Another example of this type of complexes
is [Rh [Py)3Cl3].
(iii) Complexes of the type [/W(44)2a21te : In this type
of complexes, central metal atom M is attached to two
symmetrical bidentate chelating ligands AA and two
monodentate ligands a. The two letters A and A in AA
Fig. 9.10 Cis and trans-isomers of [CoCl2(en)2] + .
indicate the two similar coordinating atoms. These
complexes exist in cis and trans forms and exhibit the
phenomenon of geometrical isomerism.
__________________________________________ _ 497
An example of this type of complex is [CoCl2(en2)]+.
The cis and trans forms of this complex are shown in
Fig. 9.10.
Other complexes of this type are [Co(en)2(NO3)2]+,
[Ir(C2O4)2Cl2] and [Ir(C2O4)2Cl2]3-. These exist in cis
and trans forms in the same way as shown above.
[B] Optical Isomerism
Optical isomerism is shown by those compounds which
posssess chirality, i.e., which do not possess any element of
*
symmetry. Presence of an element of symmetry makes a
molecule symmetric and renders it optically inactive. When
a molecule does not possess any element of symmetry, its
mirror image is not superimposable on the molecule itself.
This makes the molecule optically active. Such an asymmetric
molecule can exhibit the phenomenon of optical isomerism.
The two forms of the molecule which are mirror images of
each other are called enantiomers. One form rotates the
plane of plane polarised light in clockwise direction, while
the other in anticlockwise direction. The former is called
the d-form, while the latter is termed as Z-form.
The phenomenon of optical isomerism is quite
common in coordination compounds. The complexes whose
molecules are asymmetric exhibit optical isomerism.
The optical isomerism of various types of complexes is
discussed below.
1. Four Coordination Compounds
(i) Square planar complexes : In square planar
complexes, all the four ligands and central metal atom lie
in the same plane. Therefore, they possess a plane or axis
of symmetry and are generally not chiral in nature. This
is why optical isomerism is not common in square planar
complexes and is very rarely observed.
(ii) Tetrahedral complexes : Organic compounds
having asymmetric tetrahedral carbon atoms are
generally optically active. Therefore, it is expected that a
tetrahedral complex with four different ligands attached
to a central metal atom or ion, i.e., a complex of the type
[Mabcd]n± should exhibit optical activity. However, it has
not been possible to resolve optically active d- and Z-forms
of such a complex due to its labile nature.
Thus, optical isomerism is not very common in both
square planar as well as tetrahedral complexes. Only a very
few four coordination complexes are known which exhibit
optical isomerism.
2. Six Coordination Compounds
Optical isomerism is more common in six coordination
complexes, i.e., in octahedral complexes. Optical isomerism
of some important types of octahedral complexes is
discussed below.
1. Octahedral complexes containing only monodentate
ligands : Octahedral complexes of the type [Ma2b2c2],
[Ma2Z?2cd], [Ma2bcde] and [Mabcdef] do not possess
any element of symmetry and should be optically active.
However, none of these complexes could be resolved till
* For details, see § 10.2.7 in Unit 10.
 498 Nootan ISC Chemistry-XII

now. Theoretically, octahedral complexes containing only The d- and Z-forms along with the optically inactive trans
monodentate ligands are optically active and should exist form are shown in Fig. 9.13.
in d- and Z-forms, but the paucity of adequate experimental
techniques to resolve them makes their optical isomerism
of little value.
2. Octahedral complexes containing one or more
symmetrical bidentate chelating ligands : Octahedral
complexes containing all the monodentate ligands could not
be resolved. However, if an octahedral complex contains one
or more bidentate chelating ligands, it is possible to resolve
it into its optically active forms. Some examples of such
complexes are given below.
(i) Complexes of the type [M(AA)3]n± : In the
Optically active forms (cis)
complexes of this type, three symmetrical bidentate
chelating ligands AA are coordinated to the central metal
atom M. Such complexes do not possess any element
of symmetry and are optically active. Moreover, these
complexes can be resolved into optical isomers.
An example of this type of complexes is [Cr(C2O4)3]3-.
It is optically active and has been resolved into d-and
Z-forms (Fig. 9.11).

(OX refers to bidentate oxalato ligand.)
Other examples of this type are [Co(en)3]3+,
[Co(pn)3]3+, [Pt(en)3] + and [Cd(pn)3]2+. The optical
Optically inactive
trans form
Fig. 9.13 Optically active (cis) and optically inactive
(trans) forms of the complex [CoCl2(en)2]+.
(iii) Complexes of the type [M(AA)2ab]n± : In this
case AA are symmetrical bidentate chelating ligands, while
a and b are monodentate ligands. Such complexes exist in
three forms, two are optically active (d- and Z-forms) and
the third one is inactive meso form. An example of this type
of complexes is [CoCl(en)2(NH3)]2+. Its three forms are
shown in Fig. 9.14.

Fig. 9.12 Optically active forms of [Co(en)3]3+.

(ii) Complexes of the type [M(AA)2a2]n± : The
complexes in which two symmetrical bidentate chelating
ligands AA and two monodentate ligands a are coordinated to
central metal atom M also exhibit the phenomenon of optical
isomerism and can be resolved into their optical isomers.
An example of this type of complexes is
[CoCl2 (en)2]+. It exhibits both geometrical as well as
optical isomerism. Its cis form is unsymmetrical, while the
trans form is symmetrical because it contains a plane of
symmetry. Hence, optical isomerism is shown by cis form Fig. 9.14 Optically active and meso forms of complex
[CoCl(en)2 (NH3)]2+.
only. The cis form has been resolved into d- and Z-forms.
Coordination Compounds 499

REVIEW EXERCISES ' llllll IMIMII^—M

9.31 Illustrate : (i) Ionisation isomerism (ii) Linkage 9.45 Draw the geometrical isomers of [Pt(NH3)4CI2]2+.
isomerism and (iii) Coordination isomerism in 9.46 What type of coordination compounds show optical
coordination compounds. isomerism? Give two examples.
9.32 Explain with a suitable example geometrical
9.47 What type of isomerism is exhibited by
isomerism in coordination compounds.
[CoCl2(NH3)4]+ ? Write the structures of possible
9.33 Illustrate coordination isomerism in coordination isomers and give their IUPAC names.
compounds giving one example.
9.48 Name the type of isomerism exhibited by the
9.34 Give a chemical test to distinguish between
following pairs of compounds :
[CoBr(NH3)5]S04 and [Co(SO4)(NH3)5]Br. What
kind of isomerism do they exhibit? (i) [Co(NH3)6] [Cr(CN)6] and [Co(CN)6l[Cr(NH3)6l
9.35 Write the structures of a pair of complexes showing (ii) [Cr(H2O)6]CI3 and [Cr(H2O)5CI] Cl2 • H2O
geometrical isomerism.
(iii) [Co(NO2)(NH3)5]2+ and [Co(ONO) (NH3)5]2+.
9.36 Give the IUPAC name of the linkage isomer of
[(NH3)3PtNO2]Cl. 9.49 Write the structures of the geometrical isomers of the
9.37 Give the IUPAC name of the linkage isomer of following complexes :
[(NH3)2(H2O)PtNO2]Br. (i) [Pd(NO2)2(NH3)2]
9.38 Give the IUPAC name of the ionisation isomer of (ii) [Pt(gly)2]
[(NH3)3PtNO2]Br.
9.50 Write the IUPAC name for any of the isomers with
9.39 Write the name of the coordination isomer of the
x . the molecular formula [Pt(NH3)2Cl2]CI2.
complex [Co(en)3][Cr(CN)6].
9.40 Write the IUPAC name of the linkage isomer of 9.51 Name the ionisation isomer of [Cr(H2O)3Br]SO4.
[Co(NH3)5NO2]CI2. 9.52 Write the IUPAC name for any one of the isomers of
9.41 Write the formula for the linkage isomer of [Cr(NH3)4Cl2R.
[Cr(H2O)5SCN]2+.
9.53 Give the IUPAC name of the ionisation isomer of
9.42 How many isomers are there for the complex [Cr(NH3)4CI2]+.
[Co(NH3)4CI2]CI?
9.54 Name the geometrical isomers of [Co(en)2Cl2]+.
9.43 A coordination compound has the formula
CoCI3 • 4NH3. It does not liberate ammonia but 9.55 Describe briefly the isomerism shown by
precipitates chloride ions as silver chloride. Give the [Cr(H2O)5(NCS)]2+.
IUPAC name of the complex and write its structural
9.56 Write the IUPAC name of [Co(en)2CI2] Cl and draw
formula.
the structures of all the isomers with this formula of
9.44 Describe linkage isomerism with an example. complex.

9.4 BONDING IN COORDINATION COMPOUNDS

The first attempt to explain the nature of bonding
in coordination compounds was made by Werner in
9.4.1 Valence Bond Theory
1892. However, in the context of the modern theories of This theory was proposed by Linus Pauling and
valency, the ideas of Werner could not stand to the test is also referred to as Pauling’s theory. According to this
of time and were vindicated. Since then, several theories theory, the formation of a complex is a reaction between a
have been proposed to explain the nature of bonding in Lewis base (ligand) and a Lewis acid (metal or metal ion)
coordination compounds and to account for some of their resulting in the formation of a coordinate or dative bond
important properties such as colour, magnetic properties
between the ligands and the metal.
and geometry. Among these theories, the important ones
are Valence bond theory, Crystal field theory, Ligand field [A] Postulates of Valence Bond Theory
theory and Molecular orbital theory. In the forthcoming
discussion, we shall study the valence bond theory and The important postulates of valence bond theory are
crystal field theory in some what detail. as follows.
 500 Nootan ISC Chemistry-XII
(i) The central metal atom or ion provides a number of dsp3 or
5 Trigonal [Fe(CO)5],
vacant orbitals (equal to its coordination number) sp3d bipyramidal [MoC15],
in order to accommodate the electrons donated by [CuC15]3",
ligands. Each monodentate ligand donates a pair of [SbF5]2
electrons to the central metal atom or ion.
(ii) The vacant atomic orbitals of central metal atom d2sp3
6 Octahedral [Fe(CN)6]4"
or ion, according to the requirement, undergo a or [Fe (CN)6]3“
certain type of hybridisation. During hybridisation, 3 .2
sp a [Co(NH3)6] ,
these orbitals mix up together and redistribute their [PtCl6]2+,
energies. On account of this mixing, the same number [Cr(NH3)6]3+
of hybrid orbitals of equal energy are obtained.
Some of the common types of hybridisation, geometry
of the complexes formed and examples of complexes are [B] Structures and Shape of Some Coordination
given in Table 9.4. Compounds on the Basis of Valence Bond
(iii) When ligands approach the central atom or ion, the Theory
vacant hybrid orbitals of the central metal atom or Valence bond theory is a versatile tool to explain the
ion overlap with the orbitals of ligands containing structures and geometries of coordination compounds.
lone pair of electrons and form strong ligand-metal The structures and shape of some important coordination
coordinate covalent bonds. compounds on the basis of this theory are discussed below.
(iv) The non-bonding electrons of central metal atom 1. Octahedral Complexes
or ion remain unaffected and do not take part in The octahedral complexes are formed either by d2sp3
chemical bonding. or sp3d2 hybridisation and can be grouped into following
(v) During complex formation, the Hund’s rule of two categories.
maximum multiplicity is strictly followed. However, (a) Inner orbital complexes : The complexes involving
under the influence of strong ligands, the d2sp3 hybridisation are referred to as inner orbital complexes.
electrons may be forced to pair up against This is because the formation of such complexes involves
Hund’s rule. the participation of inner d-orbitals, i.e., (rt - 1)d-orbitals
(vi) A complex is paramagnetic, if it contains one or of the central metal atom or ion during hybridisation.
more unpaired electrons. If all the electrons in the These complexes usually contain lesser number of unpaired
complex are paired, the complex is diamagnetic in electrons. Therefore, they are also called low spin complexes
nature. or spin paired complexes. Some common examples of
Table 9.4 Hybridisation and Geometry of Some Common this type of complexes are [Fe(CN)6]4~, [Co(NH3)6]3+,
Complexes [Pt(NH3)6]4+, [Co(CN)6]4-, [Fe(CN)6]3“, etc.
(b) Outer orbital complexes : The complexes which
Geometrical involve sp3 d2 hybridisation are called outer orbital
Coordin­
Hybrid­ shape of the
ation Arrangement Examples complexes. This is because they involve the participation
isation complex
number of outer d-orbitals, i.e., nd-orbitals of the central metal
formed
atom or ion during hybridisation. Such complexes possess
2 sp Linear [Ag(NH3)2]+,
comparatively higher number of unpaired electrons.
[Ag(CN)2]~
Therefore, they are also referred to as high spin complexes
3 sp2 Trigonal [Hgi3T or spin free complexes. Some common examples of this type
planar of complexes are [Fe(H2O)6]2+, [CoF6]3-, [Cr(H2O)6]2+,
[Zn(NH3)6]2+, etc.
4 sp3 Tetrahedral [Ni(CO)4], The formation, structures and shapes of some
[MnCl4]2~, important octahedral complexes are discussed below.
[ZnCl4]2-,. (i) Hexacyanidoferrate (II) ion, [Fe(CN)6]4“ : The
[NiCl4]2+ oxidation state of iron in this complex is +2. Therefore, iron
dsp2 is present in the form of central Fe2+ ion. Six CN' ligands
Square [Pt(NH3)4]2+,
planar [Ni(CN)4]2-, are attached to this central ion. The coordination number
[Cu(CN)4]2- of Fe is six. Each CN' ligand contributes two electrons
and one negative charge to central Fe2+. Therefore, total
Coordination Compounds
number of electrons around iron nucleus is 26 - 2 + 12 =
36, and the net charge on the complex ion is +2 - 6 = - 4.
The electronic configuration of iron in the ground
state is Is2 2s2 2p6 3s2 3p6 3d6 4s2 (a in Fig. 9.15).
Therefore, the configuration of Fe2+ ion should
correspond to Is2 2s2 2p6 3s2 3p6 3d6 (b in Fig. 9.15).
At this stage all the 3d-orbitals of Fe2+ are occupied. CbT
ions are strong ligands. When six CN~ ligands approach
Fe2+, the 3d-electrons are forced to get paired up against
Hund’s rule of maximum multiplicity (c in Fig. 9.15).
Thus, two 3d-orbitals are forced to become empty. In
order to accommodate 12 electrons contributed by six
CN” ligands, central Fe2+ ion must have six vacant atomic
orbitals. Therefore, Fe provides two 3d, one 4s and three
4p orbitals for this purpose. These orbitals undergo d2sp3
hybridisation, i.e., they mix up together and redistribute
their energies. On account of this redistribution of
energy, six hybrid orbitals of equal energy are obtained
(d in Fig. 9.15). These hybrid orbitals get arranged in an
octahedral geometry around Fe2+ ion in such a way that
Fe2+ is at the centre of octahedron. These hybrid orbitals
overlap with the orbitals of CN- ligands and form stable
covalent bonds. The six hybrid orbitals accept six electron
pairs donated by six CN- ligands (e in Fig. 9.15). Thus
a stable octahedral complex ion [Fe (CN)6]4~ is formed
(finFig. 9.15).
;___________________________________________ 501
After overlapping and bond formation, all the
electrons present on the central Fe ion are paired.
Therefore, [Fe(CN)6]4~ complex ion must be diamagnetic.
This is found to be so. Moreover, since the formation of this
complex involves d sp hybridisation (i.e., inner d-orbitals
are involved), it is an inner orbital or low spin complex.
(ii) Hexacyanidoferrate (III) ion, [Fe(CN)6]3~ : The
oxidation state of Fe in this complex is +3. Hence, iron is
Q.
present as central Fe ' in this complex. It is surrounded
by six CN- ligands, each contributing two electrons to
Q.
it. Therefore, the total number of electrons around Fe
nucleus in this complex is 26 - 3 + 12 = 35, and the net
charge on it is + 3 - 6 = - 3.
Due to the involvement of d sp hybridisation, this
complex is also octahedral in shape. The complex contains
one unpaired electron. Hence it must be paramagnetic.
The ferricyanide ion has actually been found to be
paramagnetic. This is also an inner orbital complex.
3d 4s 4p
(a)
(b)
(c)

(d)

(e) tfV hybrid |U|U| T | lUIUIUIUIUlUl

® pairs electrons from six
li-e(CN)6] CN- |igands

(f) Octahedral [Fe(CN)6]3 ion :

fig. 9.15 Formation of [Fe(CN)6l4
valence bond method.
L CN J
Fig. 9.16 Formation of [Fe(CN)6]3“ complex ion by valence
bond method.
(iii) Hexaamminecobalt (III) ion, [Co (NH3)6]3+ :
This is also an octahedral complex ion formed by
d sp hybridisation. The central Co nucleus has
27 - 3 + 12 = 36 electrons in the complex and the net charge
on it is +3 + 0 = +3 because neutral ammonia ligands do not
contribute any charge to the central metal ion.
complex ion by The formation of this complex ion is shown in
Fig. 9.17.
 Nootan ISC Chemistry-XII

3d 4s 4p
(a) Cr atom iTpr111 ? I T j e iiii
3d 4s 4p
(b) Cr3+ ion I T I T 111 1 J 1—1 IIII
1_—
__ . 1
▼ d2sp 3 hybridisation
(c) cPsp3 hybrid
orbitals of 1 T | T Ltl I'T 1 1 IT'I
Cr3+ ion vacant d2sp3 hybrid orbitals

(d) cPsp3 hybrid 111 T E IUlT4-IUiniT4-lT4-l

orbitals in
[Cr(NH3)6]3+ ion 6 pairs of electrons from six
NH3 ligands
(e) Octahedral [Cr(NH3)6]3r ion :

(e) d2sp3 hybrid

orbitals in luiuiul luiuiuiuinFul
[Co(NH3)6]3+
6 pairs of electrons from six
NH3 ligands

(f) Octahedral [Co(NH3)6]3+ ion :

valence bond method.

Fig. 9.17 Formation of [Co(NH3)6]3+ complex ion by
valence bond method.
The complex ion is diamagnetic as all the electrons
present in it are paired.
Structures -'of complex ions [Co(CN)6]3” and
[Co(NO2)6]3~ are similar to that of [Co(NH3)6]3* and can
be written in the same way as shown in Fig. 9.17. They are
also octahedral complexes formed by d2sp3 hybridisation
and are diamagnetic in nature.
(iv)Hexaamminechromium (III) ion,
[Cr(NH3)6] : The oxidation state of chromium in
this complex is +3. Hence chromium is present
as Cr3+ in this complex. The central Cr3+ ion has
24 - 3 + 12 = 33 electrons, and the net charge on it is + 3 +
0 = + 3 because neutral ammonia ligands do not contribute
any charge to the central metal ion.
The formation of this complex ion is shown in Fig.
9.18.
Due to the presence of three unpaired electrons, the
complex shows paramagnetic behaviour. It is also an
inner orbital complex.
(v) Hexaaquairon (II) ion, [Fe(H2O)6]2+ : In this
complex ion, central Fe2+ ion is surrounded by six H20
ligands. Each H2O ligand contributes two electrons but no
charge (as H2O ligand is neutral) to central Fe2+ ion. The
central Fe ion thus possesses 26 - 2 + 12 = 36 electrons.
This octahedral complex ion is found to be paramagnetic
in nature and its magnetic moment indicates the presence
of four unpaired electrons in it. In order to explain this
fact, Huggins suggested that water is a weak ligand and is
n.
unable to pair up the electrons of Fe ' ion against Hund’s
rule. Hence, electrons of Fe2+ ion remain unpaired even
when six water ligands approach it. The presence of these
unpaired electrons makes it paramagnetic.
In the absence of pairing of electrons, 3d-orbitals
of Fe2+ remain occupied and are not available for
hybridisation. Therefore, in this case, Fe " makes use of
two outer 4d-orbitals and undergoes sp d hybridisation.
Q O
The formation of this complex ion by sp d hybridisation is
shown in Fig. 9.19.
Due to sp d hybridisation, this complex is octahedral
in shape. The complex contains 4 unpaired electrons which
make it paramagnetic. Since the hybridistaion in this case
involves outer d-orbitals (4d-orbitals) and the original
configuration of the metal ion is retained, it is an outer
orbital complex or a high spin complex.
Coordination Compounds 503
(e) Octahedral [CoF6]3 ion :

Fig. 9.20 Formation of [CoF6]3 complex ion by valence

bond method.
sp d hybridisation and is an outer orbital complex or
a high spin complex. Its formation is similar to that of
[Fe(H2O)6]2+ ion and is shown in Fig. 9.20.
(d) sPV
hybrid
|n| T | ? | T | T~|
EEEEEEI
orbitals 6 pairs of electrons from six The complex ion is octahedral in shape and is
in[Fe(H2O)6]2+ H2O ligands
paramagnetic in nature due to the presence of four
(e) Octahedral [Fe(H2O)6]2+ ion : unpaired electrons.

2. Tetrahedral Complexes
Tetrahedral complexes are formed by sp hybridisation.
A few examples of such complexes are [Ni(CO)4], [NiCl4]2“,
[MnCl4]2-, [CuCl4]3-, etc. Formation of [Ni(CO)4] complex
is discussed below.
Nickel carbonyl, In this complex,
[Ni(C0)4] :
Fig. 9.19 Formation of [Fe(H2O)6]2j complex ion by central nickel atom is attached to four CO ligands. The
valence bond method. oxidation state of nickel is zero. Nickel atom has the
configuration 3d84s2 (a in Fig. 9.21). In the presence
(vi) Hexafluoridocobaltate (III) ion, [CoF6]3- : In
this complex ion, central Co3+ ion is surrounded by six of strong CO ligands, rearrangement takes place
and the 4s-electrons are forced to go into 3d-orbitals
fluoride ligands. Each fluoride ligand contributes two
(b in Fig. 9.21). Thus, Ni can now provide 4s- and 4p-orbitals
electrons and one negative charge to the central ion. Thus o
for hybridisation. One 4s- and three 4p-orbitals undergo sp
the total number of electrons possessed by Co3+ ion in the
hybridisation and form four hybrid orbitals of equal energy
complex is 27 - 3 + 12 = 36 and the net charge possessed
which are directed towards the four corners of a regular
by the complex ion is +3 - 6 = -3. Fluoride is also a weak
ligand and can not pair up the electrons of Co3+ ion against tetrahedron (c in Fig. 9.21). These orbitals overlap with the
orbitals of CO ligands (d in Fig. 9.21). Thus, a tetrahedral
Hund’s rule. Therefore, this complex is also formed by
[Ni(CO)4] complex is formed (e in Fig. 9.21).
3d 4s 4p
(a) Co atom
(a)
Ni atom |T>l|T4jT4<| T | T |
IT4-I
(b) Co3’’ ion 3d 4s 4p
(b) Ni atom after the |T4<|T4<|T>L-|T4<|T>1<|
11-— 1
---- 1 1 11
(c) sp3cP hybrid rearrangement in
orbitals of the presence of strong sp3 hybridisation
Co3* ion CO ligands
vacant sp3 d2 hybrid orbitals
(c) sp3 hybrid |T4<|T4<|T>l|T4<|TJ<| I I I I I

(d) spV hybrid orbitals of Ni vacant sp3 hybrid orbitals

orbitals in
[CoF6]3-
mi t i t 111 tiimumiww i i i (d) sp3 hybrid |T4jT4<|T4<|T4<|T4<] |T4<|T4<|T4<|T4<|
6 pairs of electrons from six orbitals in [Ni(CO)4] Four pairs of electrons
F" ligands from four CO ligands
 504 Nootan ISC Chemistry-XII
(e) Tetrahedral [Ni(CO)4] complex The hybrid orbitals obtained by dsp hybridisation
assume square planar geometry. Therefore, this complex
is square planar in shape. It is diamagnetic as all the
electrons present in it are paired.
(ii) Tetracyanidocuprate (II) ion, [Cu(CN)4]2- : The
oxidation state of copper in this complex is +2. During
the formation of this complex, it is believed that the only
unpaired 3d-electron of Cu2+ ion (3d9) gets promoted
to one of the 4p-orbitals, thus making available one
Fig. 9.21 Formation of [Ni(CO)4] complex by valence vacant d-orbital. The Cu T ion, therefore, undergoes dsp
bond method. hybridisation (Fig. 9.23 d). The complex thus formed is
This complex is tetrahedral in shape. It is diamagnetic square planar and is paramagnetic due to the presence
as all the electrons present in it are paired. of one unpaired electron. The formation of this complex is
3. Square Planar Complexes shown in Fig. 9.23.
Square planar complexes are formed by dsp2 3d 4s 4p
hybridisation. Some examples of square planar
complexes are [Ni(CN)4]2’, [Cu(NH3)4]2+, [Cu(CN)4]2~,
(a) Cu atom |U|U|U|U|U| t J
[Pt(NH3)4]2t, [PtCl4] , etc. The formation of some of
3d 4s 4p
these complexes is discussed below.
(i) Tetracyanidonickelate (II) ion, [Ni(CN)4]2- : (b) Cu2‘ ion EEEEI t I
n
In this complex, the oxidation state of nickel is +2. X
Therefore, the complex consists of a central Ni2+ ion 3d 4s 4p
surrounded by CN’ ligands.
CN- ligands are strong ligands and can pair up
(c) Promotion of
unpaired 3d-electron
|t>L|T4<|T4<|T4<|
i_______
E
to a 4p-orbital dsp2 hybridisation
electrons of Ni2+ against Hund’s Rule (c in Fig. 9.22).
The pairing of1 electrons vacates one 3d-orbital of
Ni2+ ion. Thus, Ni2+ ion provides one 3d, one 4s and two (d) dsp2 hybrid eeeei
4p orbitals for complex formation and undergoes dsp2 orbitals of
vacant dsp2 hybrid orbitals
Cu2+ ion
hybridisation. The formation of this complex ion is shown
in Fig. 9.22.
Iueeei
3d 4s 4p
(e) dsp2 hybrid
orbital
EEEEI IE
(a) Ni atom EIUIHI T 1 T 1 u] in [Cu(CN)4]2“ Four pairs of electrons
from four CN~ ligands
3d 4s 4p
(b) Ni2+ ion
EEEIT111 1 rm (f) Square planar [Cu(CN)4]2 ion :
3d 4s 4p
(c) Ni2+ ion under
the influence of
EEEEI1_ | __ 1
strong CN ligands. dsp2 hybridisation

(d) dsp2 hybrid

orbitals of Ni2+ ion EEEEI
vacant dsp2 hybrid orbitals

(e) dsp2 hybrid

orbitals in
E-EEEI EEEEI □
Four pairs of electrons
[Ni(CN)4]2*
from four CN~ ligands valence bond method.
Square planar [Ni(CN)4]2- ion : 2+
The complex [Cu (NH3)4] is formed exactly in the
same way as shown above. This complex is also square
planar and is paramagnetic in nature.

[C] Magnetic Properties of Coordination

Compounds
The information regarding the structure of a metal
complex can be inferred from the value of its magnetic
2—
Fig. 9.22 Formation of [Ni(CN)4] complex ion by valence moment which can be obtained by magnetic susceptibility
bond method. measurements. In a large number of cases the predictions
Coordination Compounds
are found to be satisfactory. However, in some cases
complications are involved.
For metal ions containing upto three electrons in the
d-orbitals, e.g., Ti3+(d1), V3+(d2), Cr3+(d3), the magnetic
behaviour of the free ions and that of the complexes formed
by them are similar. In case of metal ions containing more
than three electrons in the d-orbitals, e. g., Mn3+, Cr2+(d4);
Mn2+, Fe3+(d5); and Fe2+, Co3+(d6), a vacant pair of
d-orbitals is available only when electrons get paired up
against Hund’s rule. This leaves two, one and zero unpaired
electrons respectively.
For d6 species, the magnetic data agree for several
maximum spin pairing (low spin) cases. However, for
d4 and d5 species, there are complications. For example,
[Mn(CN)6r~ shows magnetic moment of two unpaired
electrons and [CoF6]3- exhibits magnetic moment of four
unpaired electrons. [Co(C2O4)3]3- shows diamagnetic
behaviour. According to valence bond theory, this anomaly
can be explained in terms of formation of inner orbital and
outer orbital complexes. [Mn(CN)6]3~ and [Co(C2O4)]3-
are inner orbital complexes and are formed by drsp2
hybridisation. [Mn(CN)6]°~ is paramagnetic in nature
while fCo(C2O4)]3- is diamagnetic. On the other hand
[CoF6]3~ is an outer orbital complex formed by sp3d2
hybridisation. It is paramagnetic in nature and its magnetic
moment corresponds to four unpaired electrons.
|D] Strength and Limitations of Valence Bond
Theory
Till 1950s, valence bond theoy was supposed to be the
most versatile theory to explain the structure and geometry
of the coordination compounds. In fact, it was the only
one applied by chemists to coordination compounds. The
beauty of the theory is that it explains the formation,
structure and 'geometry of coordination compounds in a
very simple way. Although several more advanced theories
have been suggested and chemists have adopted them,
valence bond theory is still popular.
Limitations of Valence Bond Theory
(i) This theory does not provide a quantitative
interpretation of the stability of complexes.
(ii) The pairing of electrons against Hund’s rule under
the influence of a strong ligand is not properly
defined in this theory. The theory does not provide
a satisfactory explanation as to why at one time
the electrons must be rearranged against the
Hund’s rule, while at the other time the electronic
configuration is not disturbed. This creates
unnecessary problems in deciding the geometry of
a complex.
(iii) It is unable to interpret the absorption spectra of
complexes.
(iv) It is unable to account for the detailed magnetic
properties of complexes.
_______________________________________ 505
(v) It lacks to explain the behaviour of d8 ion (Ni2+, Pb2+,
Au3+, etc.) in forming the expected 4-coordination
complexes. Why the theory prefers square planar
structure over tetrahedral or otherwise is not very
logical.
(vi) Sometimes the theory requires the transfer of
electron from a lower energy level to a higher
energy level, which is not logical in the absence of
an energy supplier.
(vii) This theory does not give a satisfactory explanation
as to why some complexes are more labile (labile
complexes are those complexes in which one ligand
can easily be replaced by some other ligand) than
the other complexes.
(viii) It does not explain the splitting of d-orbitals of
central metal atom when ligands approach it.
9.4.2 Crystal Field Theory
The crystal field theory was originally proposed by
Bethe in 1929 to explain the nature of bonding in ionic
crystals. Later on, the theory was applied by Schlapp and
Penny (1932) and also by Van Vleck (1932) to account for
the magnetic properties of transition metal ions and their
complexes. The theory received a considerable favour from
coordination chemists and it largely replaced valence bond
theory in treating coordination compounds.
The crystal field theory assumes that the interaction
between the metal ion and the ligands is purely electrostatic
(ionic). When ligands approach central metal atom or ion,
the five degenerate d-orbitals (d-orbitals having similar
energies) of the central metal atom become differential, i.e.,
they get split up into levels of different energy under the
influence of the electrostatic field of ligands. This removes
the degeneracy of d-orbitals and they get separated into
two groups called t2g (d^, dyz, d^) and eg (dx2 _ y2, dz2)
point groups. This splitting actually depends upon the
geometry of the complex. The energy separation between
these two groups of splitted d-orbitals is usually referred
to as lODq or A. This can be estimated from spectroscopic
data and can also be calculated theoretically. Due to
repulsion of ligands, the electrons of the metal ion occupy
those d-orbitals which have their lobes farthest away from
the direction of the ligand. The occupation of electrons in
the d-orbitals is strictly according to Hund’s rule.
[A] Salient Features of Crystal Field Theory
The salient features of crystal field theory are as
follows.
(i) In a complex, the central metal atom or ion is
surrounded by various atoms or groups of atoms
called ligands.
(ii) The ligands are either negatively charged ions (like
F , Cl , CN-, etc.) or neutral molecules possessing
lone pair of electrons (like H2O, NH3, en, gly, etc.).
In neutral ligands, the most electronegative atom
points towards the central metal ion.
 506 ____________________________________________ Nootan ISC Chemistry-XII
(iii) Both metal ions and ligands act as point charges. Fig. 9.24. Among the
The interaction between the electrons of the metal five d-orbitals,
and the ligands is purely electrostatic. d9 o and d ? are
(iv) When the ligands approach central metal atom, x -y z
the electrons of central metal atom and those of axial orbitals and
ligands repel each other. These repulsive forces have maximum
destroy the degeneracy of d-orbitals and split them electron density
into two groups called t2g and es groups. This along the axes,
effect is called crystal field splitting. whereas the
The crystal field splitting depends upon the remaining three
geometry of the complex. This is because d-orbitals d-orbitals (i.e., d^,
differ in orientation. dyz and d^) are
The d-orbitals lying in the direction of ligands are planar orbitals and
affected to a larger extent while those lying in possess maximum
between the ligands are less affected. Thus, due electron density in Fig. 9.24 Octahedral geometry
to repulsion, the orbitals along the axis of ligands planes. having central metal (M) at
acquire higher energy while the orbitals lying in the centre and six ligands
From Fig. 9.24, (L) at the vertices of the
between the ligands acquire lesser energy due to it is clear that in an octahedron.
lesser repulsion. Therefore, on the approach of octahedral complex,
ligands, we have two sets of d-orbitals (of central the axial orbitals, i.e., d 2 2 and d 2 are face t0 ^ace t0
metal) having different energies. The difference in x -y
the energy between these two sets is called crystal ligands which are situated at the vertices, whereas d^, dyz
field splitting energy and is represented by A. and dzx orbitals lie in between the metal-ligand bond axes.
This is often measured in terms of an arbitrary
Therefore, ^x2_ 2 and d^2 orbitals experience the
parameter Dq and the magnitude of the splitting
energy is arbitrarily taken as 10 Dq, i.e., A = 10 Dq. maximum repulsion by the ligands while d^, dyz and d^
The exact amount of splitting energy (A or orbitals are less affected. As a result, the energy of d 2 2
10 Dq) depends upon the geometry of the complex.
(v) The electrons of the metal atom occupy splitted and d 2 orbitals is increased much more as compared to
d-orbitals strictly in accordance to Hund’s rule.
The electrons first occupy those d-orbitals which the remaining three d-orbitals. Thus, the five degenerate
suffer less repulsion, i.e., the orbitals which have d-orbitals lose their degeneracy and split into two point
their lobes farthest away from the direction of groups, t2s and eg. t2g group of orbitals contain three
ligands. degenerate d^, dyz and dzx orbitals, whereas eg group of
(vi) The theory- does not take into account any orbitals contain two degenerate d 2 2 and orbitals.
x -y
overlapping between the orbitals of central metal
atom and those of ligands. Hence, the theory Due to face to face repulsion, eg group of orbitals possess
totally rules out the possibility of any covalent higher energy than those of t2g orbitals. The energy gap
character in the complex. (crystal field splitting) in between these two sets is Ao or
(vii) The stability of a complex can quantitatively 10 Dq (the subscript o in Ao refers to octahedral geometry).
be known by the magnitude of crystal field The crystal field splitting in case of an octahedral
.
stabilisation energy *(CFSE) The magnitude of complex is shown in Fig. 9.25.
CFSE depends upon the nature and number of
ligands and also upon the geometry of the complex. dx2 _ y2 dz2(eg)
_OO
|B] Applications of Crystal Field Theory to the 0 6Ao f
poooo —£ ------ Ao or 10Dq
Complexes of Different Geometries / degenerate
d-orbitals of
1. Octahedral Complexes OOQQQ- z- the metal ion in dXy dyz d2x (t2g)
In an octahedral complex, six ligands occupy their Five degenerate the crystal field splitting of d-orbitals
d-orbitals of the (Hypothetical) in the octahedral
positions at the six vertices of a regular octahedron with
central metal ion crystal field
metal atom at the centre of the octahedron as shown in in the absence of
ligands
* The crystal field stabilisation energy (CFSE) is actually the gain in
energy achieved by preferential filling up of orbitals by electrons. It should be Fig. 9.25 Splitting of d-orbitals in an octahedral crystal field.
expressed as a negative quantity, i.e., CFSE < 0. The zero value of CFSE signifies Here Ao = lODq, 0.6 Ao = 6 Aq and 0.4 Ao = 4 Dq.
that the complex is not stable.
Coordination Compounds______________
Calculations have shown that in this case, the energy
of the t2g orbitals is less by an amount 0.4 Ao or 4 Dq
as compared to the energy of hypothetical degenerate
d-orbitals in crystal field while those of eg orbitals is more
by an amount 0.6 Ao or 6 Dq than those of hypothetical
degenerate d-orbitals in crystal field. Calculations have also
shown that each electron entering into t2g orbital stabilises
the complex by 0.4 Ao or 4 Dq while each electron entering
into eg orbital destabilises the complex by 0.6 Ao or 6 Dq.
The total gain of energy obtained by filling the electrons in
d-orbitals gives the crystal field stabilisation energy (CFSE).
The stability of the complex depends upon this energy.
The magnitude of Ao or 10 Dq depends upon the
strength of ligands. When ligand field is strong, the splitting
is large and consequently the value of Ao is high. In case
of a weak ligand field, the splitting is comparatively less
and consequently the value of Ao is also less. Therefore,
the filling of electrons in d-shell depends upon whether the
ligand field is strong or weak.
Ligands can be arranged in a series in the order of
increasing field strength as given below.
T < Br~ < SCN" < Cl " < S2~ < F~ < OH" < C2O24 < H2O
<NCS~ < EDTA4" < NH3 < en < CN" < CO
Such a series is termed as spectrochemical series. It
is an experimental series and is based upon the absorption
of light by complexes with different ligands.
507
In octahedral complexes with d1 configuration, the
only d electron occupies t2g orbital and stabilises the
complex by -0.4 Ao or -4 Dq. The CFSE in to case
would thus be -4 Dq. Similarly in complexes with d and
d3 configurations, the electrons will occupy t2g orbitals
and will remain unpaired. The CFSE in these cases would
respectively be -8 Dq and -12 Dq. In the octahedral
complex with d4 configuration, the fourth electron cannot
go to eg orbital because 10 Dq is large and is greater than
P. Hence, this electron has to be paired up in one of the t2g
orbitals. The CFSE in this case would be
CFSE = 4 x (-4 Dq) + 1 x P = -16 Dq + P
Similar is the situation with octahedral complexes with
configuration d 5 and d 6. The fifth and sixth electrons in
these complexes will also get paired up in t2g orbitals. The
CFSE in these cases will be -20 Dq + 2 P and -24 Dq + 3 P
respectively.
Table 9.5 Arrangement of Electrons in Octahedral Com­
plexes and Corresponding CFSE in Strong
No. of d High No. of
electrons Low energy
energy eg unpaired CFSE
in the . t2g orbitals orbitals electrons
metal ion
d1 T 1 - 4 Dq

Filling up of Electrons in d-Orbitals d2 t t 2 -8 Dq

The electrons get filled up in the splitted d-orbitals in d3 T •t t 3 - 12 Dq
accordance to the following rules :
d4 U T t 2' - 16 Dq +P
(i) Electrons fill up the splitted d-orbitals strictly in
accordance to Hund’s rule of maximum multiplicity, d5 U u t 1 - 20 Dq + 2 P

e., electrons prefer to occupy vacant orbitals of lower

i. d6 u u 0 - 24 Dq + 3 P
energy. d7 u u u T 1 - 18 Dq + 3 P
(ii) In case of-a strong ligand field, when Ao (10 Dq) d8 u H t T 2 - 12 Dq + 3 P
is large and greater than the pairing energy P (the T
energy required by the electrons to get paired up),
d9 u ti U 1 - 6 Dq + 4 P

i.e., 10 Dq > P, electrons get paired up in low energy d10 u n U u 0 0 Dq + 5 P

t2g orbitals instead of going to higher energy eg 7
In octahedral complexes with d configuration, the
orbitals. The complex thus obtained contains a majority
of paired electrons and possesses low spin. Such a seventh electron has no other way than to go to a higher
complex is called a low spin complex. energy e orbital. This electron destabilises the complex by
6 Dq. Therefore, the CFSE in this case would be
(iii) In case of a weak ligand field Ao (10 Dq) is small and
CFSE = 6 x ( — 4 Dq) + (1x6 Dq) + 3P = —18 Dq + 3P
less than the pairing energy P, i.e., 10 Dq < P The
This type of complexes contain only one unpaired
electrons thus prefer to go to higher energy eg levels
and tend to remain unpaired as far as possible. The electron. In the same way octahedral complexes with
complex thus obtained may possess high spin and is d8 d9 and d10 configurations would have CFSE equal to
called a high spin complex. - 12Dq + 3P, - 6Dq + 4P, and 0 Dq + 5P respectively. The
arrangement of electrons in all possible type of octahedral
(i) Arrangement of electrons in a strong ligand field (Low
complexes corresponding CFSE and number of unpaired
sPin octahedral complexes): The strong ligands such as CO,
CT, NO2, en, NH2 etc., cause large splitting of d-orbitals. electrons possessed by them are shown in Table 9.5.
Therefore, the values of Ao or 10 Dq is greater than that of (ii) Arrangement of electrons in a weak ligand field
Pairing energy P, i.e., Ao (10 Dq) > P. Thus, the electrons (High spin octahedral complexes) : Weak ligands like H2O,
Prefer to get paired up in lower t2g orbitals instead of going OH" cr Br", r, etc., cause only a very small splitting
10 higher eg orbitals.
 508
Nootan ISC Chemistry-XII
of d-orbitals. Therefore, the value of Ao or 10 Dq is small
2. Tetrahedral Complexes
and much less than the pairing energy P, i.e., 10 Dq < P.
In a tetrahedral
Therefoie, in this case electrons prefer to go to high energy
complex, the four ligands
eg orbitals instead of getting paired up in low energy t2g are placed at the four
orbitals. corners of a regular
The octahedral complexes with d1, d2 and d3 tetrahedron while the
configurations have the same distribution of electrons as in metal is placed at the
case of^strong ligand field. The configuration of complexes centre of tetrahedron as
shown in Fig. 9.26.
with d are different. Now the fourth electron goes to eg
From the geometry
orbital and remains unpaired. Therefore, a d4 complex
of the complex, it is clear
possesses four unpaired electrons in a weak ligand field. that ligands approach
The CFSE of a d4 complex would thus be the central metal atom in Fig. 9.26 Tetrahedral
CFSE = 3 x (-4 Dq) + (1 x 6 Dq) = - 6 Dq. between the three geometry having central
Similarly in case of d5 complexes, the fifth electron coordinate axes. metal atom (M) at the
Therefore, the orbitals centre and four ligands
will also remain unpaired in eg orbital and the complex (L) at the four corners.
d^, dyz) d^ (t2g orbitals) (
will contain five unpaired electrons. The CFSE can be lying in different planes
calculated in the same way and comes out to be equal to are now pointed towards ligands while the axial orbitals
CFSE = 3 x (- 4 Dq) + (2 x 6 Dq) = 0 Dq. 2 2 and d 2 (e„ orbitals) lie in between the metal-
x y z &
In case of d6 octahedral complexes, the sixth electron
ligand bond axes. Hence t2g orbitals experience much more
has no other option than to get paired up in one of t2g
repulsion by the ligands as compared to that experienced
orbitals. This type of complexes will thus have four by eg orbitals. Due to greater repulsion, the d^, dyz and
unpaired electrons with CFSE equal to dzx orbitals are now of higher energy while d 2_ 2 and
* y
CFSE = 4 x (- 4 Dq) + (2x6 Dq) + P - - 4 Dq + P.
The configuration of d7, ds, d9 and d10 type octahedral d 2 orbitals are of comparatively lower energy. Moreover,
complexes can be obtained similarly. The electronic since the orbitals do not interact directly with the ligand
arrangements in all possible types of octahedral complexes orbitals, the splitting of d levels is much less as compared
in weak ligand field with corresponding CFSE and number to octahedral ligand field splitting.
of unpaired electrons have been shown in Table 9.6. The crystal field splitting of d-orbitals in a tetrahedral
Table 9 6 Arrangement of Electrons in Octahedral Com- ligand field is shown in Fig. 9.27.
Table 9.6 ^angand Coiresponding CFSE in Weak Ligand
dxy dyz dzx (t2g)
Field

d High No. of
No. of
electrons
Low energy energy eg unpaired CFSE OOOOQ/L . L
t2g orbitals orbitals electrons / degenerate
in the '■■Too l10Dq
d-orbitals of
metal ion the metal ion in ^x2-y2’ ^z2 (eg)
1 -4Dq OOOOO the crystal field splitting of d orbitals
Five degenerate (Hypothetical) in the tetrahedral
2 -8 Dq d-orbitals of the
d2 T central metal ion
ligand field
3 - 12 Dq
T in the absence of
d3 ligands
T 4 - 6 Dq
d* tT t Fig. 9.27 Splitting of d-orbitals in a tetrahedral crystal
T 5 0 Dq field. Here At = 10 Dq, 0.4 A( = 4 Dq and 0.6 At = 6 Dq.
ds t
t 4 -4Dq +P Calculations have shown that t2g orbitals are raised by
d6 f
T 3 - 8 Dq + 2P 4 Dq, whereas eg orbitals are lowered by 6 Dq as compared
d7 n Ti t t T 2 -12 Dq + 3P
to the energy of hypothetical degenerate d orbitals in
d8 u U Tl n T 1 - 6 Dq + 4P
ligand field. The energy gap, i.e., the crystal field splitting 1

d? u
U between the two sets is At or 10 Dq (the subscript t in Af I
s
Q Dq + 5P
T4 n n 0 refers to tetrahedral geometry).
e
d10 T4
Coordination Compounds

Calculations have also shown that each electron
entering into low energy eg orbitals stabilises the complex
by 6 Dq, whereas each electron entering into high energy
t2g orbitals destabilises it by 4 Dq.
The distribution of electrons in these orbitals depends
on whether the ligand field is strong or weak. In a strong
ligand field, electrons prefer to get paired up in low energy
orbitals in place of going to high enregy t2g orbitals.
Thus, we shall have a low spin complex. But if the ligand
field is weak, the electrons would like to go to high energy
t2g orbitals in place of being paired up in low energy eg
orbitals and we shall have a high spin complex.
|C| Colour in Coordination Compounds
Coordination compounds exhibit a wide range of
colours. The sensation of colour is produced when light
having a wavelength within the visible region (400 nm -
750 nm) of electromagnetic spectrum strikes the retina
of the eye. A complex shows colour when the white light
passing through it is partly absorbed and partly reflected.
The colour shown by the complex is the complementary
colour generated from the wavelengths present in the
partly reflected light. For example, if complex absorbs
green light, it shows red colour. The relationship between
the wavelength of the light absorbed and the colour shown
by some complexes is given in Table 9.7.
Table 9.7 Relationship between the Wavelength of Light
Absorbed and the Colour Shown by Some Com­
plexes
Complementary
Wavelength Colour of
colour shown
Complex species of light the light
by the complex
absorbed absorbed
species
[Co(CN)6]3" 310 nm Ultraviolet Pale yellow
[Co(NH3)6]3+ 475 nm Blue Yellow orange
[Ti(H2O)6]3+ 498 nm Yellow Purple
green
[Co(NH3)5(H20)]3+ 500 nm Blue green Red
[CoC1(NH3)5]2+
535 nm Yellow Violet
[Cu(H2O)4]2+ 600 nm Red Blue
The colour shown by a complex can easily be explained
on the basis of crystal field theory. According to the crystal
field theory, colour of complexes is due to d-d transitions
of electrons. For example, the violet colour of [Ti(H2O)6]3+
can be explained as follows.
[Ti(H2O)6]3+ is an octahedral complex. The central
metal ion Ti3+ constitutes a 3d1 system. The only electron
present in the 3d-subshell lies in the t2g level in the ground
state of the complex. The next higher state available is
empty eg level. When the complex absorbs light from the
yellow green region, the electron present in the lower
t2g level gets excited to the higher eg level. Thus, a d-d
transition takes place as shown in Fig. 9.28.
— — eg
— — ----- kg - ----- ----- kg
Ground state Excited state
f2g eg p1
'2g eg
Fig. 9.28 d-d transition in [Ti(H2O)6]3+.
On account of this transition, the complex appears
violet in colour.
In the absence of ligands, there is no crystal field
splitting and hence the substance is colourless. For
example, if water is removed from [Ti(H2O)6]3+ by
heating, it becomes colourless. Similarly CuSO4 • 5H2O is
blue in colour, whereas anhydrous CuSO4 is white.
[D] Limitations of Crystal Field Theory
1. Crystal field theory assumes that metal-ligand
interaction is purely electrostatic. This assumption
can not be said to be very realistic.
2. The theory takes into account only the d-orbitals
of central metal atom or ion and their splitting is
studied; the other orbitals, e.g., s and p orbitals of
central metal are not taken into.account.
3. The theory is unable to explain why a certain
ligand causes a large splitting while the other a
small, e.g., the theory has no explanation why H2O
is a stronger ligand than OH-.
4. This theory rules out the possibility of any
7i-bonding in complexes. This is a serious
drawback of the theory because 7t-bonding is
found to exist in complexes.
5. The theory does not give any weightage to the
orbitals of ligands. Therefore, all properties
related to ligand orbitals and their interaction
with metal orbitals remain unexplained.
[E] Superiority of Crystal Field Theory Over
Valence Bond Theory
Inspite of all the above limitations, crystal field theory
has an edge over valence bond theory. The crystal field theory
is supposed to be superior to valence bond theory due to
following facts.
1. Crystal field theory provides the fine details of
magnetic properties of the complexes and gives a
suitable explanation of the variation of magnetic
moments with temperature. These fine details are
not provided by VBT.
2. Crystal field theory provides a quantitative
measure of the stability of a complex. With this
measure, the geometry acquired by a particular
 510 ‘_____________________________________
complex can be predicted. VBT does not provide
any such measure.
3. Crystal field theory gives an explanation for
certain thermodynamic and kinetic properties
of complexes. VBT does not provide such an
explanation.
Nootan ISC Chemistry-XII
4. The observed d-d transitions in complexes and
their colour can be explained only on the basis
of crystal field theory. The VBT neither explains
spectroscopic properties nor gives an adequate
explanation for the colour of complexes.

9.5 STABILITY OF COORDINATION COMPOUNDS IN SOLUTION (STABILITY

CONSTANT)
The thermodynamic stability of a complex depends Factors Affecting the Stability of a Complex
upon the extent of interaction between the metal ion and The thermodynamic stability of a complex depends
ligands. If the interaction is strong, the complex formed upon the following factors.
would be thermodynamically more stable. (i) Charge density on the central metal ion : The
As we have seen earlier, the reaction between a metal stability of a complex depends upon the charge density
ion and a ligand can be regarded as a Lewis-acid base on the central rnetal ion which in turn depends upon the
reaction. Suppose a metal ion Ma+ interacts with n ligands magnitude of charge and the radius of the ion, i.e., charge/
Lx~ to form a complex [MLn]b+, where a, x and b represent radius ratio. Higher the magnitude of charge and smaller the
the charges on the metal, ligand and complex respectively. size of ion, more is the charge density on the ion and greater
The reaction between the metal ion and ligands can be is the stability of the complex.
described by the following equilibrium. For example, the magnitude of positive charge
Ma+ + nLx~ [MLn]b+ on Cu2-r and Cd2+ ions is the same but the ionic radius
The equilibrium constant for the above equilibrium is of Cu ion (69 pm) is less than that of Cd ion (97
pm). Obviously, the charge density on Cu2*- is greater
termed as the stability constant and is represented by K.
than that on Cd2’r ion because the former has a higher
It is given by
charge/radius ratio. This is why complexes formed by
K [MLJ^ Cu2* ion are more stable than those formed by Cd2+ ion
[Ma+][L*-]n as is clear from the data given above (K for [Cu(NH3)4]2+
= 4.5 x 1011; K for [Cd(NH3)4]2+ =1.3 x 107).
The stability constant is an important parameter of
a complex. It may be used to express the thermodynamic Ionic radii of some bivalent metal ions are given
stability of a complex because it gives an indication of the below :
stability of the complex in solution. Higher the value of Ion Cu2+ Ni2+ Co2+ Fe2+ Mn2+ Cd2+
stability constant, greater is the thermodynamic stability Ionic radius
of the complex in solution. 69 78 82 83 91 97
(pm)
The values of stability constant for some common
complexes in solution are given below. Therefore, with the same ligand, the stability of
System Stability constant (X) complexes formed by these ions follows the following
order:
Cd2+ + 4NH3 [Cd(NH3)4]2+ 1.3 x 107 Cu2+ > Ni2+ > Co2+ > Fe2+ > Mn2+ > Cd2+
Ag+ + 2 NH3 [Ag(NH3)2]+ 1.6 x 107 ------- Stability of complexes decreases------- >
(ii) Nature of ligands : Ligands are Lewis bases because
Cu2+ + 4NH3 [Cu(NH3)4]2+ 4.5 x 1011 they act as electron donors during the formation of a
complex. Therefore, the stability of a complex should
Ag+ + 2 CN~ [Ag(CN)2]" 5.5 x 1018
depend upon the ease with which the ligands donate lone
Cu2+ + 4 CN“ [Cu(CN)4]2~ 2.0 x 1027 pairs of electrons to the central metal ion, i.e., on the basic
strength of the ligand. Hence, greater the basic strength of
Co3+ + 6 NH3 [Co(NH3)6]3+ 5.0 x 1033 the ligand, greater is the stability of the complex.
For example, CN- is more basic than NH3. Therefore,
The above values of stability constant indicate that cyanido complexes of a metal ion are more stable than its
the cyanido complexes are more stable than the ammine ammine complexes as is evident from the following data :
K for [Ag(CN)2F = 5.5 x 1018;
complexes. Hence, it may be concluded that CN- is a stronger
ligand than NH3. K for [Ag(NH3)2]+ = 1.6 x 107.
Coordination Compounds
9.6 IMPORTANCE AND APPLICATIONS (USES) OF COORDINATION COMPOUNDS
Metal ions coordinate with a variety of molecular species
to form complexes which possess different physicochemical
properties. This ability of metal ions to enter into complex
formation has been exploited in many ways and has been
used for a variety of purposes. Some important applications
are given below.
(i) In analytical chemistry : Formation of coordination
compounds is largely used in analytical chemistry for the
qualitative detection and quantitative estimation of metal
ions. Some examples are given below.
(a) In the first group of qualitative analysis, the
precipitate containing AgCl, Hg2Cl2 and pbcl2 is treated
with aqueous ammonia solution to separate Ag+ ions from
2+ 2+
Hg2 and Pb ions. AgCl forms a complex with ammonia
and passes into the solution as given below.
AgCl + 2NH3 [Ag (NH3)2] Cl
Hg2Cl2 and PbCl2 remain undissolved as they do not
form complexes with ammonia. This helps in the detection
of Ag+ ions.
(b) In the ILA group of qualitative analysis, Cd2+ are
9-4-
tested in the presence of Cu ions by complex formation.
The solution containing both Cu2+ and Cd2+ ions is treated
with excess of KCN, when both the ions form their cyanido
complexes.
Cu2+ + 4CN“ [Cu (CN)4]2-
Cd2+ + 4CN“ [Cd (CN)4]2“
Since [Cu (CN)4]2- is more stable than [Cd(CN)4]2-,
the solution contains a higher equilibrium concentration
of Cd2+ ions. Therefore, on passing H2S, only CdS gets
Precipitated. Thus, Cd2+ ions can easily be detected in the
9i
Presence of Cu ions.
(c) Ni ions can easily be detected and estimated by
complexing them with dimethylglyoxime.
(ii) For the estimation of hardness of water: The hardness
°fwater is due to the presence of Ca2+ and Mg2+ ions in it. The
^xadentate ligand EDTA (ethylenediaminetetraacetato)
forms stable complexes with Ca2+ and Mg2+ ions, and
can be used for the estimation of hardness of water by
simple titration method. Further, Ca2+ and Mg2+ ions can
k selectively estimated by this method because of the
difference in the stability constants of their EDTA complexes
(K for Ca2+ - EDTA complex = IO10'7; K for Mg2+ - EDTA
complex = IO8'70).
(iii) In the extraction of metals : The technique of
complex formation is widely used in the extraction of noble
metals like silver and gold. For example, in the extraction
of silver from its ores, the finely powdered ore is treated
with a dilute solution of KCN when the metal present in the
ore forms a cyanido complex and passes into the solution.
The solution is then treated with zinc. Zinc being more
electropositive displaces silver from the complex.
Ag2S + 4NaCN^=± 2Na [Ag (CN)2] + Na2S
Sodium dicyanoargentate (I)
2Na[Ag(CN)2] + Zn ----- > Na2 [Zn (CN)4] + 2Ag
Sodium tetracyanozincate (II)
(iv) In electroplating : Since complexes are quite stable
and dissociate in solution to a very small extent, they give a
controlled supply of metal ions in the solution. This property
of complexes has been used in the electroplating of noble
metals like silver and gold. The complex, K [Ag(CN)2] is
widely used as an electrolyte in the electroplating of inferior
metals by silver. Similarly, the complex, K[Au(CN)2] is used
for gold plating.
(v) In medicine : Complexes have also been used
in medicine. For example, the platinum complex,
cis-[PtCl2(NH3)2] known as cisplatin has been found
useful in the treatment of cancer.
(vi) In modifying the redox behaviour of metal ions :
The redox behaviour of a metal ion may be modified by
complexing it with a particular type of ligand. For example,
cobalt is easily oxidised from +2 to +3 state in the presence
of some ligands. This property is utilised by many enzymes
containing metal ions (e.g., Mo, Cu, Fe) to perform catalysed
biochemical reactions.
(vii) Biological importance : Several coordination
compounds play significant roles in a number of processes
occurring in plants and animals. Several biologically
important natural compounds are complexes. For example,
chlorophyll present in plants is a complex of magnesium;
haemoglobin present in blood is a complex of iron; vitamin
B12 is a complex of cobalt.
■
512
REVIEW
9.57 Using valence bond theory of complexes explain
the geometry and diamagnetic nature of ion
[Co(NH3)6]3+.
9.58 Describe the hybridisation scheme, the resultant
geometry and the magnetic behaviour of
[Co(NH3)6]3+.
9.59 How would you account for the following?
(i) [Ti(H2O)6]3+ is coloured, while [Sc(H2O)6]3+ is
colourless.
(ii) [Fe(CN)6] is weakly paramagnetic, while
|Fe(CN)6]4‘ is diamagnetic.
(iii) [Ni(CO)4] possesses tetrahedral geometry, while
n_
[Ni(CN)4] is square planar.
9.60 Using valence bond approach, predict the shape and
magnetism (i.e., paramagnetic or diamagnetic) of
[Co(CN)4]“.
9.61 Using valence bond approach, predict the shape
and magnetism (paramagnetic or diamagnetic) of
[Ni(CN)4]2-.
9.62 Following valence bond scheme, explain the bonding
in [Cr(H2O)6]3+.
9.63 What do you understand by the term stability
constant, K of a complex? Knowing that the value of
K for [Cu(NH3)4]2+ is 4.5 x 1011 and for [Cu(CN)4]2-
is 2.0 x 1027, suggest (a) which complex species will
furnish less Cu2+ ions in solution, and (b) which out
of NH3 and CN~ is a stronger ligand.
9.64 Select a complex formation reaction and write an
expression for the stability constant of the complex
species. What information is conveyed regarding the
strengths of ligands from the stability values of their
complexes with a metal ion? Illustrate your answer
with examples of monodentate ligands.
9.65 Using the valence bond approach, explain the shape
and magnetic behaviour of [Ni(NH3)6]2+.
9.66 On passing H2S through a solution containing Cu2+
and Cd2+ ion and excess of KCN solution, only Cd
gets precipitated. Explain.
9.67 Draw the structure and write the hybridisation state of
the central atom of each of the following species:
(i) |Co(NH3)6]3+
(ii) [NiCI4]2".
9.68 Describe the following :
(i) Linkage isomerism with an example.
(ii) Magnetic behaviour of [Ni(CO)4] ion.
Nootan ISC Chemistry-XII
EXERCISES
9.69 Explain the square planar shape of the
tetracyanidonickelate (II) ion and account for its
magnetic property.
9.70 Using the valence bond approach, predict the shape
and magnetic character of [Ni(CO)4].
9.71 Deduce the shape and magnetic behaviour of the
complex ion [Co(NH3)5NO2]2+.
9.72 Explain the following observation :
Tetrahedral Ni(ll) complexes are usually
paramagnetic but square planar Ni(ll) complexes are
diamagnetic.
9.73 What magnetic behaviours are expected for
[Ni(CO)4] and [NiCI4]2- and why?
9.74 Giving an example, describe how the formation
of coordination compounds is useful in analytical
chemistry.
9.75 Using the valence bond approach, deduce the shape
and magnetic character of [Cr(CO)6],
9.76 Using the valence bond approach, predict the shape
and magnetic character of [Fe(CN)6] ion.
9.77 Write the neutral molecule in which the central
atom is sp d hybridised.
9.78 Using valence bond theory, deduce the geometry
and magnetic nature of [Ni(CN)4]2~.
9.79 Draw a figure to show splitting of degenerate
d-orbitals in an octahedral crystal field. How does
the magnitude of Ao decide the actual configuration
of d-orbitals in a complex entity?
9.80 Compare the magnetic behaviour of the complex
entities [Fe(CN)6]4- and [FeF6]3-.
9.81 (a) Thevaluesofdissociationconstantof[Cu(NH3)4]2’r
and [Co(NH3)6]3+ are 1.0 x ,10-12 and
6.2 x 10~34 respectively. Which complex would
be more stable and why?
(b) Using valence bond theory of complexes,
explain the geometry and magnetic nature of
[Ni(NH3)6]2+.
9.82 (a) Name two properties of the central metal ion
which enable it to form stable complex entities.
(b) The formation of complex compounds, finds
application in the extraction of some metals.
Furnish one example to support the above
statement.
9.83 Draw a sketch to show the splitting of d-orbitals in
an octahedral crystal field.
Coordination Compounds 513

9.7 BONDING IN METAL CARBONYLS

The homoleptic carbonyls in which carbon monoxide metals. These carbonyls have simple well defined structures.
(CO) acts as the ligand are formed by most of the transition The structures of some metal carbonyls are given in Fig- 9.29.

Fig. 9.29 Structure of some metal carbonyls.

As shown in Fig. 9.29, tetracarbonylnickel(0) is

tetrahedral, pentacarbonyliron(0) is trigonal bipyramidal
and hexacarbonylchromium (0) is octahedral.
Decacarbonyldimanganese (0) is made up of two square
pyramidal Mn(CO)5 units joined by a Mn-Mn bond, while
octacarbonyldicobalt(0) has a Co—Co bond bridged by
two CO groups.
Bonding in Metal carbonyls
Bonding in metal carbonyls can be explained on the
basis of molecular orbital theory. According to this theory,
following two types of overlap take place between the
orbitals of metal and those of CO molecule.
(a) o-overlap : First, a dative overlap of a filled o-orbital
of carbon of CO occurs with vacant orbital of the metal
resulting in the formation of a dative cr-bond. During the
formation of this bond, the lone pair of electrons on the C
atom of the CO ligand is donated to the metal atom. The
formation of dative o-bond is shown in Fig. 9.30(a).
Fig. 9.30 (a) o-overlap resulting in the formation
(b) rc-overlap : After the formation of dative c-bond, a of metal<-CO dative n-bond (b) 7t-overlap
filled d-orbital of metal overlaps with a vacant antibonding resulting in the formation of metal -> CO
a* orbital of CO as shown in Fig. 9.30(b). This overlap dative 7t-bond (The shaded orbitals represent
results in the formation of a dative n-bond. This type of filled orbitals).
bonding is also known as back bonding. Thus, a metal-CO
o-orbital of carbon. At the same time, the formation of a
bond can be represented as
dative o-bond drifts the electrons into the orbitals of metal.
„, , Dative o-bond__
Metal < — CO This makes CO positive and increases the acceptor strength
Dative n-bond of n-orbitals. Hence, the c>-bond formation strengthens
Due to the formation of dative n-bond, the metal the ^-bonding and vice-versa. This type of bonding creates
electrons are drifted into CO orbitals. This drift makes a synergic effect which stabilises the metal carbonyl. It is
CO as a whole negative and increases its basicity via the supported by the vibrational spectra of carbonyls.
 r

__________________________________________ Nootan ISC Chemistry-XII

REVIEW EXERCISES '

9.84 Describe the nature of bonding in metal carbonyls. (ii) the o' and n-bonds present, and
9.85 Draw the structure of Fe(CO)5. (iii) the electrophilic and nucleophilic centres in it.
9.86 Draw the structure of a carbonyl group and indicate 9.87 Draw the structures of:
clearly (i) Ni(CO)4
(i) the hybridised state of carbon, (ii) Fe(CO)5

SELF ASSESSMENT AND COMPETITION FILE

The Basic Concepts at a Glance
1. Coordination compounds are those molecular or addition
Name of
compounds in which a central metal atom or ion is permanently / Oxidation x
Number the central
attached to certain atoms or groups of atoms called ligands. Name of state in
and name metal ion
2. The ligands are capable of donating at least a pair of the cation Roman
of ligands with suffix
electrons to the central metal atom or ion and get attached to it Numerals^
ate
by coordinate bond.
e.g., K[Ag(CN)2] is named as potassium dicyanidoargentate (I).
3. Coordination compounds retain their identity even in
12. Coordination compounds exhibit various types of
solution and their properties are different from those of their
constituent atoms or groups. isomerism. Among these ionisation isomerism, hydrate isomerism,
4. A positively charged complex ion is called cationic complex linkage isomerism, coordination isomerism, ligand isomerism,
ion (e.g., [Ag(NH3)2]+), whereas a negatively charged complex ion geometrical isomerism, optical isomerism are significant.
is called anionic complex ion (e.g., [CuCI4]2-). 13. According to the Valence bond theory, the hybridised
vacant orbitals of the central metal atom or ion overlap with
5. The part of a coordination compound consisting of central
the orbitals of ligands containing lone pair of electrons and form
metal and ligands directly attached to it is called the coordination
strong ligand-metal coordinate covalent bonds. During complex
sphere, while the part which gets ionised in solution is called the ionic
formation, the Hund's rule of maximum multiplicity is strictly
sphere of the complex.
followed. However, under the influence of strong ligands, the
6. The maximum number of ligands which can be coordinated
electrons may be forced to pairup against Hund's rule.
to a central metal atom or ion is called the coordination number of 14. A complex is paramagnetic, if it contains one or more
the central metal atom or ion. unpaired electrons. If all the electrons in the complex are paired,
7. Modern notation for representing coordination the complex is diamagnetic in nature.
compounds is as follows. 15. The state of hybridisation of the central metal atom
present in some complexes, their geometry and magnetic nature
For cationic complexes : [Metal atom; anionic, neutral,
are as follows.
cationic ligands] ionisable groups
For anionic complexes : lonisable groups [Metal atom; Hybridisation
anionic, neutral, cationic ligands] state of the Geometry of
Complex Magnetic nature
8. When more than one type of ligands are present in a central metal the complex
complex, they are named in the alphabetical order regardless of atom
the nature of charge present on them. [Fe(CN)6]4— d2sp3 Octahedral Diamagnetic
9. A bridging ligand is indicated by adding the prefix p. before [Fe(CN)6]3” d2sp3 Octahedral Paramagnetic
the name of the ligand.
[Co(NH3)6]3+ ,2 3
10. While naming a cationic complex, following sequence is d sp Octahedral Diamagnetic
observed. [Cr(NH3)6]3+ .2 3
d sp Octahedral Paramagnetic
Common
/Oxidationy [Fe(H2O)6]2+ sp3d2 Octahedral Paramagnetic
Number name of
state in Name of
and name the central [CoF6]3" sp3d2 Octahedral Paramagnetic
Roman the anion
of ligands metal atom [NiCI4]2- sp3
k numerals J Tetrahedral Paramagnetic
or ion
[Ni(CO)4] sp3 Tetrahedral Diamagnetic
e.g., [Cu(NH3)4] SO4 is named as tetramminecopper [Ni(CN)4]2’ dsp2 Square Diamagnetic
(II) sulphate. planar
11. Following sequence is observed while writing the name [Cu(CN)4]2- dsp2 Square Diamagnetic
of an anionic complex.
planar
Coordination Compounds 515

16. The complexes involving d sp hybridisation are called
inner orbital complexes. These complexes usually contain lesser
number of unpaired electrons. Therefore, they are also called
low spin complexes or spin paired complexes. Some examples of
this type of complexes are [Fe(CN)6]4- [Co(NH3)6]3', [Co(CN)6]4-,
(Fe(CN)6]3-, etc.
The complexes involving spa^ hybridisation are called outer
orbital complexes. They possess comparatively higher number of
unpaired electrons. Therefore, they are also referred to as high spin
complexes or spin free complexes. Some examples of this type of
complexes are [Fe (H2O)6]2+, [CoF6]3~, [Cr(H2O)6]2+, [Zn(NH3)6]2+,
17. According to the Crystal field theory, the interaction
between the metal ion and the ligands is purely electrostatic. On
the approach of ligands, the five degenerate d-orbitals of the
central metal atom get split into two point groups-t2g (dxy, dyz, dzx)
2
ande„(d2 2, dz ). The splitting depends upon the geometry of
y x —y
the complex. The energy separation between these groups is
referred to as 10 Dq or A. The occupation of electrons in splitted
d-orbitals is in accordance to Hund's rule.

etc.

VERY SHORT ANSWER TYPE QUESTIONS

1. Sort out the complex salts and double salts among the 20. Write the geometrical isomers of the complex [PtBrCKNH3)2].
following : Pot. dicyanidoargentate (I), Mohr’s salt, Potash 21. Write the cis- and trans-isomers of the complex
alum, Pot. ferrocyanide. [CoCI2(en)(NH3)4]+.
2. Does a solution of K4[Fe (CN)6] contain Fe2+ ions ?
22. Write the geometrical isomers of [CoCI2(en)(NH3)2]+.
3. Name the ions present in the aqueous solution of 23. Do square planar complexes exhibit optical isomerism?
K2SO4 • AI2(SO4)3 • 24H2O. 24. Write the optical isomers of [Cr(C2O4)3]3-.
4. What is a ligand? Give two examples. 25. Write the optically active isomers of [Co(en)2CI2]+.
5. Sort out the cationic, anionic and neutral complexes among 26. Why is the trans-isomer of [Co(en)2CI2]+ not optically active ?
the following :
27. Name the hybridisation state of the central metal ion in the
K2[Hgl4], [Co(NH3)6]CI3, K3[Fe(CN)6], [Ni(C0)4], following complexes :
[Pt(NH3)2CI2], [Fe(H2O)6]CI3.
(i) [Co(NH3)6]CI3 (ii) [Pt(NH3)2CI2]
6. Name the ligand/ligands present in [Pt(NH3)2CI2]Br2. Q O
28. State whether a complex formed by sp d hybridisation is a
7. What is the oxidation number of Co in [Co(NH3)5NO2]CI2?
low spin or a high spin complex.
8. Give one example each of neutral, anionic and cationic 29. The complex [Cr(NH3)6]3+ involves d2sp3 hybridisation of the
ligands.
central metal ion. State whether it is an inner orbital or an outer
9. Give two examples each of monodentate and didentate
orbital complex.
ligands.
30. How is the stability constant K of a complex related to its
10. Give the names of the following ligands : OH-, H2O, NH3,
thermodynamic stability?
NH2CH2—CH2NH2, CN-, NCS-.
31. Among NH3 and ON-, which is a stronger ligand ?
11. Write the names and the structures of any two chelating 32. The ionic radii of Cu2+, Ni2r and Fe2+ ions are 69, 78 and 83
ligands.
pm respectively. Arrange these ions in the decreasing order of
12. What is the number of coordination sites in
the stability of the complexes formed by them.
(a) oxalato (b) ammine 33. Name the reagent generally used to estimate the hardness of
(c) ethylenediamine (d) EDTA? water.
13. What is the number of ionisable chlorine atoms in the 34. Name a complex used in the treatment of cancer.
complex CoCI3 • 4NH3? 35. Name the metals present in haemoglobin, chlorophyll and
14. How many ions would be furnished by the complex vitamin B12.
CoCI3 ■ 6NH3 in aqueous solution? 36. Complete the following statements for the coordination entity
15. Calculate the charge number of the complex ion furnished by (complex ion) [CrCI2(OX)2]3-.
the complex K2[Hgl4]. (a) OX is abbreviation for.................
16. Write the IUPAC names of the following complexes : (b) The oxidation number of chromium is.................
(a) [Fe(H2O)6]CI3 (b) [CoCI2(en)2] (c) The coordination number of chromium is.................
17. Write the IUPAC name of the complex (d) .............. is a bidentate ligand.
[CoCI(NO2)(NH3)4]CIO4. 37. Specify the oxidation number of the metals in the following
18. Write the structures of the following complexes : coordination entities :
(a) [Co(CN)(H2O)(en)2]2+ (b) [PtCI4]2-
(a) ammonium diamminetetra (thiocyanato-N) chromate (III)
(b) dichloridobis (ethylenediamine) cobalt (IV) sulphate. .(c) [CrCI3(NH3)3] (d) [CoBr2(en)2]+
19. What type of isomerism is exhibited by the following pairs of (e) K3[Fe(CN)6],
isomers? 38. Specify which out of the following complex structures exhibit
(i) [Pt(OH)2(NH3)4]SO4 and [Pt(SO4)(NH3)4](OH)2 geometrical isomerism :
(ii) [Cr(SCN)(H2O)5]2+ and [Cr(NCS)(H2O)5]2+ (a) linear (b) square planar
(iii) [Cu(NH3)4][PtCI4] and [Pt(NH3)4][CuCI4] (c) tetrahedral (d) octahedral.
 516 Nootan ISC Chemistry-XII
39. How many geometric isomers are possible in the following 40. What is the coordination entity formed when excess of KCN
coordination entities? is added to an aqueous solution of copper sulphate? Why is
(a) [Cr (OX)3]3" (b) [CoCI3(NH3)3] it that no precipitate of copper sulphide is obtained when
H2S (g) is passed through this solution?

Hints and Answers

1. Complex salts: Pot. dicyanidoargentate(l), Pot. ferrocyanide 23. Not commonly
Double salts : Mohr’s salt, Potash alum 26. It possesses a plane of symmetry and is achiral.
2. No 27. (i) d2sp3 (ii) dsp2
3. K+, Al3+, SO2"
28. High spin complex
5. Cationic : [Co (NH3)6] Cl3, [Fe (H20)6] Cl3;
29. Inner orbital complex
Anionic : K2[Hgl4], K3[Fe (CN)6];
31. CN"
Neutral: [Ni (C0)4], [Pt (NH3)2 Cl2]
32. Cu2+> Ni2+> Fe2+
6. Ammine (NH3), Chloride (Cl)
7. +3. 33. EDTA
12. (a) 2 (b) 1 (c) 2 (d) 6 34. Cisplatin
13.one 35. Fe, Mg, Co
14. Four 36. (a) oxalato ligand (b) + 3 [x - 2 + 2 (- 2) = - 3,
15. -2 x = + 3] (c) six (d) oxalato (OX)
16. (a) hexaaquairon (III) chloride 37. (a) +3 (b) + 2 (c) + 3 (d) + 3 (e) + 3
(b) bis(ethylenediamine) cobalt (II) chloride.
38. Square planar and octahedral
17. tetraamminechloronitrocobalt (III) perchlorate
39. (a) Nil (b) Two
18. (a) NH4 [Cr (NCS)4 (NH3)2]
(b) [CoCI2 (en)2] SO4 40. CuS04 + 4KCN ----- > K2 [Cu(CN)4] + K2SO4. The
coordinate entity formed is [Cu(CN)4]2~. This entity is stable and
19. (i) Ionisation isomerism
does not dissociate/ionise to give Cu2+ ions. Hence, no precipitate
(ii) Linkage isomerism
(iii) Coordination isomerism is formed on passing H2S through its solution.

SHORT ANSWER TYPE QUESTIONS

1. What are coordination compounds? Explain with suitable (iii) Fe in K3[Fe(CN)6];
examples. (iv) Co in [Co(NH3)3(H2O)2CI]".
2. Give the ionisation behaviour of the following salts : 12. Give the names of the following ligands :
(i) Potash alum (ii) Pot. argentocyanide (i) NH2 (ii) ONO- (iii) [CH3]3P
(iii) Mohr’s salt.
(iv) NO2 (v) NH2CH2CH2NH2.
3. Define the following terms in relation to coordination
• compounds : 13. Give the IUPAC names of the following complexes :
(i) Ligands (ii) Complex ion (i) [Cu(NH3)4]SO4 (ii) [CoCI2(en)(NH3)2]+
(iii) Coordination sphere (iv) Coordination number. (iii) [Co(en)2CI2] (iv) K3[AI(C2O4)3]
4. What are ligands and how are they classified on the basis of (v) [Co(NH3)6][CdCI5],
charge? Give suitable examples. 14. Write the formulae of the following complexes :
5. How are ligands classified on the basis of the number of (i) potassium tetraiodidomercurate (II)
donor atoms? Give an example of each type. (ii) hexaaquairon (II) sulphate
6. What is meant by monodentate and bidentate ligands? (iii) sodium ethylenediaminetetraacetatonickelate (III)
Illustrate with examples. (iv) hexaamminecobalt (III) chloride.
7. What do you understand by chelating ligands and chelates? 15. Explain and illustrate with an example each of the following
Illustrate with suitable examples. in relation to coordination compounds :
8. Describe briefly the main postulates of Werner’s theory. (i) Ionisation isomerism (ii) Hydrate isomerism.
9. Write the structures of the following complexes on the basis 16. Explain the term ‘linkage isomerism’ with respect to
of Werner’s theory : coordination compounds and illustrate with two examples.
(i) CoCI3 ■ 6NH3 (ii) CoCI3 • 5NH3 17. When does coordination compounds show coordination
(iii) CoCI3 ■ 3NH3. isomerism? Explain with suitable examples.
10. Represent the following complexes according to the IUPAC 18. Define geometrical isomerism in relation to coordination
conventions : compounds. Write the geometrical isomers of
(i) CoCI3 • 5NH3 (ii) CoCI3-4NH3 (i) [PtCI2(NH3)2] (ii) [Co(NH3)4CI2],
(iii) CoCI3 • 6NH3 (iv) PtPyNH3CIBr. 19. Write the structures of cis- and trans-isomers of the following
11. Calculate the oxidation number of complexes :
(i) Au in H [AuCI4J; (i) [Pd(NH3)2(NO2)2] (ii) [Pt(gly)2]
(ii) Ag in K[Ag(CN)2]; (iii) [Co(en)2CI2] .
Coordination Compounds
20. Why is optical isomerism not common in square planar and
tetrahedral complexes?
21. What type of complexes exhibit optical isomerism? Write
the structures of the optical isomers of [Co(en)3]3+.
22. Write the structures of optical isomers of the following
complexes :
(i) [Co(en)2CI2]+ (ii) [CoCI2(en)(NH3)2].
23. Write the structures of all the possible stereoisomers of the
complex [CoCI(en)2(NH3)]2+.
24. What are the basic assumptions of valence bond theory in
relation to coordination compounds?
25. Name the geometrical shapes of the complexes involving
following types of hybridisation :
(i) sp3 (ii) dsp2
(iii) sp3d2 (iv) d2sp3.
26. What do you understand by inner orbital and outer orbital
complexes? Give one example each.
27. What are low spin and high spin complexes? Illustrate your
answer with suitable examples.
28. Explain the structure, geometry and magnetic behaviour
of the complex K3 [Fe (CN)6] on the basis of valence bond
theory.
29. On the basis of valence bond theory, predict the magnetic
behaviour of the following complexes :
(i) [Co(NH3)6]3+ (ii) [Fe(H2O)6]2+
(iii) [Ni(NH3)4]2+.
30. Discuss the formation of [Ni(CO)4] on the basis of valence
bond theory.
31. Explain why [Ti(H2O)6]3+ is coloured, while [Sc(H2O)6]3+
colourless.
3—
32. Explain the structure of [FeF6] on the basis of valence bond
theory.
33. Explain the structure of [Cu(NH3)2]2+ on the basis of valence
bond theory.
34. What are the limitations of valence bond theory?
35. Write a note on the stability of coordination compounds in
solution.
36. Discuss the main factors which affect the stability of a
complex in solution.
37. How does the presence of a particular ligand affect the
thermodynamic stability of a complex? Illustrate your answer
with a suitable example.
38. What is the role of KCN in the test of Cd2+ ion in the presence
of Cu2+ ion?
39. Name the reagent used for the detection and estimation of
Ni2+ ions. Write the equation.
40. How is the technique of complex formation useful in the
extraction of metals? Explain with an example.
41. What is meant by the denticity of a ligand? Give examples of
a unidentate and a bidentate ligand.
Hints and Answers
11. (i) +l+x + (-l)x4 = 0,x = +3
r- (ii) +1 +x + (-1) x 2 = 0, x = +1
I (iii) +3 + x + (-1) x 6 = 0, x = +3
(iv) x + (0) x 3 + (0) x 2 - 1 = +1, x = +2.
_______________________________________ __ 517
42. Using IUPAC norms, write the formulae for the following :
(a) tetrahydroxozincate(ll)
(b) hexaamminecobalt (III) sulphate
(c) potassium tetrachloridopalladate (II)
(d) potassium tri (oxalato) chromate (III)
(e) diamminedichloridoplatinum (II)
(f) hexaammineplatinum (IV)
(g) potassium tetracyanidonickelate (II)
(h) tetrabromidocuprate (II)
(i) pentaamminenitrito-O-cobalt (III)
(j) pentaamminenitrito-N-cobalt (III).
43. Using IUPAC norms, write the systematic names of the
following :
(a) [Co(NH3)6]CI3
(b) [CoCI(NO2)(NH3)4]CI
(c) [Ni(NH3)6]CI2
(d) [PtCKNH2CH3)(NH3)2]CI
(e) [Mn(H2O)6]2+
(f) [Co(en)3]3+
(g) [Ti(H2O)6]3+
(h) [NiCI4]2“
(i) [Ni(C0)4].
44. Draw the structures of optical isomers of:
(a) [Cr(OX)3]3 (b)TPtCI2(en)2]2+
(c) [CrCI2(en)(NH3)2]+.
45. Draw all the isomers (geometric and optical) of:
(a) [CoCI2(en)2]+ (b) [CoCI(en)2(NH3)]2+
(c) [CoCI2(en)(NH3)2]+.
46. Draw the structures of:
(a) cis-dichloridotetracyanidochromate (III)
(b) /Wer-triamminetrichloridocobalt (III) '
(c) Fac-triaquatrinitro-N-cobalt (III).
47. Write the correct formulae for the following coordination
compounds :
(a) CrCI3 • 6H2O (violet, with 3 chloride ions/unit formula)
(b) CrCI3 • 6H2O (light green colour, with 2 chloride ions/unit
formula)
(c) CrCI3 • 6H2O (dark green colour, with 1 chloride ion/unit
formula).
48. For the octahedral complexes of Fe3 ' in SCN”(thiocyanato-S)
and in CN- ligand environments, the difference between
the spin-only magnetic moments in Bohr magnetons (when
approximated to the nearest integer) is [Atomic number of
Fe = 26] (J.E.E. Ad., 2015)
49. If the freezing point of a 0.01 molal aqueous solution of
a cobalt (III) chloride-ammonia complex (which behaves as
a strong electrolyte) is -0.0558°C, the number of chloride(s)
in the coordination sphere of the complex is [ Kf of water =
1.86 K kg mol-1] (J.E.E. Ad., 2015)
50. The number of geometric isomers possible for the complex
[CoL2CI2r (L = H2NCH2CH2O") is. (J.E.E. Ad., 2015)
13. (i) tetraamminecopper (II) sulphate
(ii) diamminechloridoethylenediaminecobalt (III) ion
(iii) dichloridobis (ethylenediamine) cobalt (II)
(iv) potassium trioxalatoaluminate (III)
(v) hexaamminecobalt (III) pentachloridocadmate (II)
 Nootan ISC Chemistry-XII
14. (i) K2[Hgl4] (ii) [Fe(H2O)6] S04 (h) tetrachloridonickelate (II) ion
(iii) Na2[Ni(EDTA)] (iv) [Co(NH3)6]CI3 (i) tetracarbonylnickel (0).
31. Ti (III) contains an unpaired electron, whereas Sc (III) has
no unapaired electron.
39. dimethylglyoxime,

CH3—C = NOH

CH3— C= NOH
Dimethylglyoxime

OH 0
T
ch3-—C=N N=C—CH3
1 1
ch3 —C=N XN = C—CH3

0 OH
Nickel dimethylglyoxime (Red)

Mer-triamminetrichloridocobalt (III)
42. (a) [Zn(OH)4]1
2~ (b) [Co(NH3)6]2(SO4)3

(c) K2[PdCI4] (d) K3[Cr(OX)3]

(e) [PtCI2(NH3)2] (f) [Pt(NH3)5]4+
(g) K2[Ni(CN)4] (h) [CuBr4]2'
(i) [Co(ONO)(NH3)5]2+
(j) [Co(N02)(NH3)5]2+
43. (a) hexaamminecobalt (III) chloride Fac-triaquatrinitro-N-cobalt (III)
(b) tetraamminechloridonitritocobalt (III) chloride
47. (a) [Cr(H2O)6]CI3
(c) hexamminenickel (II) chloride
(b) [CrCI(H2O)5]CI2 • H2O
(d) diamminechlorido (methylamine) platinum (II) chloride
(c) [CrCI2(H2O)4]CI • 2H2O
(e) hexaaquamanganese (II) ion
48. 4
(f) tris (ethylenediamine) cobalt (III) ion
49. 1
(g) hexaaquatitanium (III) ion
50. 5

ESSAY (LONG ANSWER) TYPE QUESTIONS

1. What are the coordination compounds? Explain the following 9. Wnat is stability constant? Explain its significance in predicting
terms in relation to coordination compounds : the thermodynamic stability of a complex in solution. Discuss
(i) central metal ion the factors which affect the stability of a complex.
(ii) coordination and ionic spheres 10. Discuss the important applications of coordination
(iii) coordination number. compounds.
2. What are ligands and how are they classified? Explain with 11. Explain on the basis of valence bond theory, the experimental
suitable examples. finding that [Ni(CN)4]2- ion with a square planar structure is
3. Giving suitable examples, discuss the various types of diamagnetic and the [NiCI4]2" ion with tetrahedral geometry
structural isomerism exhibited by coordination compounds. is paramagnetic.
4. Giving suitable examples, discuss the geometrical isomerism 12. What postulates did Werner use to explain the bonding in
shown by following types of complexes : coordination compounds? What is the main weakness of
(\)[Ma2b2]n± (ii) [Ma2bc\n *
Werner’s theory?
(iii) [M(AB)2]n ±.
13. Discuss the nature of bonding in the following coordination
5. What type of complexes exhibit optical isomerism ? Discuss
entities on the basis of valence bond theory.
the optical isomerism shown by the complexes of the type (a) [Fe (CN)6]45 8"
7
6 (b) [FeF6]3 ~
[M(AA)2a2]n± and [M(AA)a2b2]. Give suitable examples.
(c) [Co (OX)3]3 " (d) [CoF6]3 ’
6. What are the salient features of the valence bond theory?
Explain the structure and magnetic behaviour of 14. Discuss briefly the role of coordination compounds in :
hexaamminenickel (II) ion on the basis of this theory. (a) biological systems
7. Discuss the salient features of crystal field theory. Why is this (b) analytical chemistry
theory regarded superior to valence bond theory? (c) medicinal chemistry, and
8. Apply crystal field theory to octahedral and tetrahedral
(d) extraction metallurgy of metals.
complexes.
Coordination Compounds 519

OBJECTIVE (MULTIPLE CHOICE) TYPE QUESTIONS

Choose the correct option in the following questions.
1. Coordination number of Fe in K4[Fe(CN)6] is 16. The hardness of water is estimated by
(a) 2 (b) 3 (c) 4 (d) 6. (a) conductivity method (b) EDTA method
2. The complex [Co(NH3)5Br]SO4 will give white precipitate (c) titrimetric method (d) distillation method.
with 17. A complex involving dsp hybridisation has
(a) BaCI2 (b) AgNO3 (c) KI (d) none. (a) a square planar geometry (b) a tetrahedral geometry
3. [Cr(NH3)6]3+ ion is (c) an octahedral geometry (d) trigonaI planar geometry.
(a) paramagnetic (b) diamagnetic 18. In the compound, lithium tetrahydroaluminate, the ligand is
(c) square planar (d) tetrahedral. (a) H+ (b) H
4. The coordination number and oxidation number of X in (c) IT (d) none of these.
[X(S04)(NH3)5]CI is 19. Which of the following ligands does form a chelate?
(a) 10 and 3 (b) 2 and 6 (c) 6 and 3 (d) 6 and 4. (a) Acetate . (b) Oxalate
5. K3[CoF6] is a high spin complex. The hybridisation state of (c) Cyanide (d) Ammonia.
Co in this complex is 20. The geometry of Ni(CO)4 and Ni(PPh3)CI2 are
(a)sp3d (b) dsp2 (c) sp3d2 (d) d2sp3. (a) both square planar
6. Which of the following is most likely the structure of (b) tetrahedral and square planar respectively
CrCI3 • 6H2O if one third of total chlorine of the compound is (c) both tetrahedral
precipitated by adding AgNO3 to its aqueous solution? (d) square planar and tetrahedral respectively.
(a) CrCI3 • 6H2O (b) [CrCI(H2O)5jCI2 • H2O 21. Which of the following complex species does involve d2sp3
(c) [CrCI2(H2O)4]CI • 2H2O (d) [CrCI3(H2O)3] • 3H2O. hybridisation?
7. Amongst [Ni(C0)4], [Ni(CN)4]2“ and [NiCI4]2“ (a) Linkage (b) Ionisation
(a) [Ni(C0)4] and [NiCI4]2- are diamagnetic and [Ni(CN)4]2” (c). Hydrate (d) Coordination.
. is paramagnetic. 22. Type of isomerism shown by [Cr(NH3)5NO2]CI2 is
(b) [NiCI4]2~ and [Ni(CN)4]2~ are diamagnetic and [Ni(C0)4] (a) linkage isomerism (b) hydrate isomerism
is paramagnetic. (c) ligand isomerism (d) none of these.
(c) [Ni(CO)4] and [Ni(CN)4]2~ are diamagnetic and [NiCI4]2“ 23. Coordination number of Fe in K4[Fe(CN)6] is
is paramagnetic. (a) 2 (b) 4 (0 6 (d) 10.
(d) [Ni(C0)4] is diamagnetic and [NiCI4]2- is paramagnetic. 24. The complex ion which has no ‘d’ electrons in the central
8. The name of [Cr(NH3)4 Cl2] NO3 is metal atom is
(a) [Mn04] (b) [Co(NH3)6]3+
(a) tetraamminodichloridochromium (III) nitrate
(c) [Fe(CN)5]3~ (d) [Cr(H2O)6]3+.
(b) tetraaminodichloridochromium (II) nitrate
(c) dichloridotetraamminechromium (II) nitrate (l.i.T. Screening, 2001)
(d) tetraamminedichloridochromium (III) nitrate. 25. The IUPAC name of K3[Co(NO2)6] is
9. Which one of the following has tetrahedral geometry? (a) potassium (I) hexanitrocobaltate (II)
Fe(CO)
(a) 5' (b) [Co(NH3)6]2+ (b) potassium (III) hexanitrocobaltate (III)
(c)[NiCI4]2“ (d) [Ni(CN)4]2-. (c) potassium hexanitrocobalt (0)
(d) potassium hexanitrocobaltate (III).
10. The number of geometrical isomers for [Pt (NH3)2 Cl2] is
26. Among the following ions, which one has the highest
(a) two (b) one (c) three (d) four. paramagnetism?
11. Which of the following complexes is likely to show optical (a) [Cr(H2O)6]3+ (b) [Fe(H2O)6]2+
activity? (c) [Cu(H2O)6]2+ (d) [Zn(H2O)2]2+.
(a) [Cr(H2O)6]3+
27. Which of the following give maximum number of isomers?
(b) trans-[Co(NH3)2(en)2]3 (a) [Co(NH3)4CI2] (b) [Ni(en)(NH3)4]2+
(c) trans-[Co(NH3)4CI2]+ (c) [Ni(C2O4)(en)2] (d) [Cr(SCN)2(NH3)4]+.
(d) cis-[Co(NH3)2(en)2]3\ 28. Coordination number of Ni in [Ni(C2O4)3]4_ is
12. [Co(NH3)4CI2]NO2 and [Co(NH3)4CI(NO2)]CI are
(a) 3 (b) 6 (c) 4 (d) 5.
(a) geometrical isomers (b) optical isomers
29. The species having tetrahedral shape is
(c) linkage isomers (d) ionisation isomers. (a) [PdCI4]2- (b) [Ni(CN)4]2’
13. The number of ions formed when [Cu(NH3)]4SO4 is dissolveu (c) [Pd(CN)4]2- (d) [NiCI4]2“. (I.I.T., 2004)
in water is
30. Which of the following compounds is not coloured ?
(a) 1 (b) 2 (c) 4 (d) zero. (a) Na2[CuCI4] (b) Na3[AIF6]
14. Metal present in chlorophyll is (c) K4[Fe(CN)g] (d) K3[Fe(CN)6].
(a) zinc (b) magnesium 31. The IUPAC name of [Co(en)2CI2]CI is
(c) calcium (d) sodium. (a) bis(ethylenediamine)dichloridocobaltdll) chloride
15. Wilkinson’s catalyst is (b) dichloridobis(ethylenediamine)cobalt(lll) chloride
(a) Ni (b) [(C6H5)3P]3 RhCI (c) dichloridobis(ethylenediamine)cobalt(l) chloride
(c) LiAIH4 (d) Fe2O3. (d) trichloridobis(ethylenediamine)cobalt (0).
520 ___________________________________________ Nootan ISC Chemistry-XII
32. The correct order of hybridisation of the central atom in 41. Which of the following compounds shows optical isomerism ?
following species NH3, [PtCI4]2^, PCI5, BCI3 is (At. No. (a) [Co(CN)5]3“ (b) [Cr(C2O4)3]3-
Pt = 78) (c) [ZnCI4]2“ (d) [Cu(NH3)4]2+.
2 3 3 2 (A.I.E.E.E., 2005)
(a) dsp2, dsp3, sp and sp (b) sp , dsp2, dsp3, sp
42. Which one of the following cyanido complexes would exhibit the
(c) dsp2, Sp2, dsp3, sp3 (d) dsp2, sp3, sp2, dsp3.
lowest value of paramagnetic behaviour ?
(I.I.T. Screening, 2001) (a) [Co(CN)6]3’ (b) [Fe(CN)6]3-
33. Consider the following complex : (c) [Mn(CN)6]3~ (d) [Cr(CN)6]3~.
[Co(NH3)5C03]CI04.
(Atomic no. Cr = 24, Mn = 25, Fe = 26, Co = 27)
The coordination number, oxidation number, number of
(A.I.E.E.E., 2005)
d-electrons and number of unpaired d-electrons on the metal
43. The value of the spin only magnetic moment for one of the
are respectively
following configurations is 2.84 BM. The correct one is
(a) 6, 3, 6, 0 (b) 7, 2, 7, 1
(a) d5 (in strong ligand field)
(c)
7, 1,6, 4 (d) 6, 2, 7, 3.
34. The most stable ion is (b) d (in weak as well as in strong fields)
(a) [Fe(OH)5]3“ (b) [FeCI6]3“ (c) d4 (in weak ligand field)
(c) [Fe(CN)6]3~ (d) [Fe(H2O)6]3+. (d) d4 (in strong ligand field). (A.I.E.E.E., 2005)

(A.I.E.E.E., 2002) 44. The IUPAC name for the complex [Co(NO2)(NH3)5] Cl2 is
35. One mole of the complex compound Co(NH3)5CI3, gives 3 (a) nitrito-N-pentaaminecobalt (III) chloride
moles of ions on dissolution in water. One mole of the same (b) nitrito-N-pentaamminecobalt (II) chloride
complex reacts with two moles of AgN03 solution to yield (c) pentaamminenitrito-N-cobalt (II) chloride
(d) pentaamminenitrito-N-cobalt (III) chloride.
two moles of AgCl (s). The structure of the complex is
(A.I.E.E.E., 2006)
(a) [Co(NH3)5CI]CI2
45. Nickel (Z = 28) combines with a uninegative monodentate
(b) [Co(NH3)3 Cl3] -2NH3 ligand X“ to form a paramagnetic complex [NiX4]2-. The
(c) [Co(NH3)4CI2]CI ■ NH3
number of unpaired electron(s) in the nickel and geometry of
(d) [Co(NH3)4CI]CI2 • NH3. . (A.I.E.E.E., 2003)
this complex ion are respectively
36. The coordination number of a central metal atom in a complex
(a) one, tetrahedral (b) two, tetrahedral
is determined by
(a) the number of ligands around a metal ion bonded by (c) one, square planar (d) two, square planar.
sigma bonds (A.I.E.E.E., 2006)
(b) the number of ligands around a metal ion bonded by pi- 46. The coordination number and the oxidation state of the
bonds element ‘E’ in the complex [E(en)2(C2O4)]NO2 (where (en) is
(c) the number of ligands around a metal ion bonded by ethylenediamine) are, respectively
sigma and pi-bonds both
(a) 6 and 2 (b) 4 and 2
(d) the number of only anionic ligands bonded to the metal
(c) 4 and 3 (d) 6 and 3.
ion. (A.I.E.E.E., 2004)
(A.I.E.E.E., 2008)
37. Which one of the following complexes is an outer orbital
47. In which of the following octahedral complexes of Co (at.
complex?
(a) [Fe(CN)6]4’ (b) [Mn(CN)6]4~ no. 27), will the magnitude of Ao be the highest?
(c) [Co(NH3)6]3+ (d) [Ni(NH3)6]2+. (a) [Co(CN)6]3’ (b) [Co(C2O4)3]3’
(c) [Co(H2O)5]3+ (d) [Co(NH3)6]3+.
(A.I.E.E.E., 2004)
38. Coordination compounds have great importance in biological (A.I.E.E.E., 2008)
systems. In this context which of the following statements is 48. Which of the following complex ions is not expected to absorb
incorrect? visible light?
(a) Chlorophylls are green pigments in plants and contain (a) [Ni(CN)4]2- (b) [Cr(NH3)6]3+
calcium. (c) [Fe(H2O)6]2" (d) [Ni(H20)6]2r.
(b) Haemoglobin is the red pigment of blood and contains (A.I.P.M.T., 2010)
iron. 49. The existence of two different coloured complexes with the
(c) Cyanidocobalamin is vitamin B12 and contains cobalt. composition of [Co(NH3)4CI2F is due to
(d) Carboxypeptidase-A is an enzyme and contains zinc.
(a) linkage isomerism
(A.I.E.E.E., 2004)
(b) geometrical isomerism
39. Which one of the following has largest number of isomers?
(a) [Ru(NH3)4CI2]+ (b) [Co(NH3)5CI]2+ (c) coordination isomerism
(c) [lr(PR3)2H(CO)]2+ (d) [Co(en)2CI2]+. (d) ionisation isomerism. (A.I.P.M.T., 2010)
50. The d-electron configurations of Cr2+, Mn2+, Fe2+ and Co2'
(/? = alkyl group, en = ethylenediamine) (A.I.E.E.E., 2004)
are d4, d5, d6 and d7 respectively. Which one of the following
40. The correct order of magnetic moments (spin only values in
BM) among the following is will exhibit minimum paramagnetic behaviour?
(a) [MnCI4]2- > [CoCI4r > [Fe(CN)6]4“ (At. no. Cr = 24, Mn = 25, Fe = 26, Co = 27)
(b) [MnCI4]2" > [Fe(CN)6]4^ > [CoCI4]2’ (a) [Fe(H2O)6]2+ (b) [Co(H2O)6]2+
(c) [Fe(CN)6]4^ > [MnCI4]2~ > [CoCI4]2’ (c) [Cr(H2O)6]2+ (d) [Mn(H2O)6]2+.
(d) [Fe(CN)6]4- > [CoCI4]2- > [MnCI4]2-. (A.I.E.E.E., 2004)
(A.I.P.M.T., 2011)
Coordination Compounds 521
51. The complexes [Co(NH3)6][Cr(CN)6] and [Cr(NH3)6] 62. Which one of the following complexes shows optical
[Co(CN)6] are the examples of which type of isomerism? isomerism?
(a) Ionisation isomerism (b) Coordination isomerism (a) [Co(NH3)3CI3] (b) c/s[Co(en)2CI2]CI
(c) Geometrical isomerism (d) Linkage isomerism. (c) trans[Co(en)2CI2]CI (d) [Co(NH3)4CI2]CI
(A.I.P.M.T., 2011) (en = ethylenediamine) (J.E.E. Main, 2016)
52. The complex, [Pt(Py)(NH3)BrCI] will have how many 63. Among [Ni(C0)4], [NiCI4]2-, [Co(NH3)4CI2]CI, Na3[CoF6],
geometrical isomers? Na202 and CsO2, the total number of paramagnetic
(a) 4 (b) 0 (c) 2 (d)3. compounds is
(A.I.P.M.T., 2011) (a) 2 (b) 3
53. Which one of the following is an outer orbital complex and (c) 4 (d) 5 (J.E.E. Ad., 2016)
exhibits paramagnetic behaviour? 64. Which of the following has longest C—0 bond length? (Free
(a) [Ni(NH3)6]2+ (b) [Zn(NH3)6]2+ C—0 bond length in CO is 1.128 A.)
(c)[Cr(NH3)6]3+ (d) [Co(NH3)6]3+. (a) Ni(C0)4 (b) [Co(C0)4]
(A.I.P.M.T., 2012) (c) [Fe(CO)4]2" (d) [Mn(C0)6]+
54. Among the following complexes, the one which shows zero (N.E.E.T., 2016)
crystal field stabilisation energy (CFSE) is 65. The correct order of the stoichiometries of AgCI formed
(a) [Mn(H2O)6]3+ (b) [Fe(H2O)6]3+ when AgNO3 in excess is treated with the complexes :
(c) [Co(H2O)6]2+ (d) [Co(H2O)6]3+. CoCI3 • 6NH3, CoCI3 • 5NH3, CoCI3 ■ 4NH3 respectively is
(A.I.P.M.T., 2014) (a) 1 AgCI, 3 AgCI, 2 AgCI (b) 3 AgCI, 1 AgCI, 2 AgCI
55. Which of the following complexes is used to be as an (c) 3 AgCI, 2 AgCI, 1 AgCI (d) 2 AgCI, 3 AgCI, 1 AgCI
anticancer agent? (N.E.E.T., (UG)-2017)
(a) mer-[Co(NH3)3CI3] (b) cis-[PtCI2(NH3)2] 66. Correct increasing order for the wavelengths of absorption in
the visible region for the complexes of Co3+ is
(c) cis-/<2[PtCI2Br2] (d) Na2CoCI4.
(A.I.P.M.T., 2014) (a) [Co(en)3]3+, [Co(NH3)6]3+, [Co(H2O)6]3+

56. Which of the following complex species is not expected to (b) [Co(H2O)6]3+, [Co(en)3]3+, [Co(NH3)6]3+
exhibit optical isomerism? (c) [Co(H2O)6]3+, [Co(NH3)6]3+, [Co(en)3]3+
(a) [Co(en)3]3+ (b) [Co(en)2CI2]+ (d) [Co(NH3)6]3+, [Co(en)3]3+, [Co(H2O)6]3+
(c) [Co(NH3)3CI3] (d) [Co(en)(NH3)CI2]+. (N.E.E.T., (UGJ-2017)
□_
(J.E.E. Main, 2013) 67. Pick out the correct statement with respect [Mn(CN)6]
57. The octahedral complex of a metal ion M3+ with four 3 2.
(a) It is sp d hybridised and octahedral
monodentate ligands Llt L2, L3 and L4 absorb wavelengths 3 2
(b) It is sp d hybridised and tetrahedral
in the region of red, green, yellow and blue respectively. The 2 3
(c) It is d sp hybridised and octahedral
increasing order of ligand strength of the four ligands is
(a) L4 < L3 < L2 < /-i (b) Ly < L3 < L2 < t4 (d) It is dsp hybridised and square planar
(N.E.E.T., (UG)-2017)
(c) L3 < L2 < L4 < Z-i (d) < L2 < L4 < L3.
68. On treatment of 100 mL of 0.1 M solution of CoCI3 • 6H?O
(J.E.E. Main, 2014)
o_ with excess AgNO3; 1.2 x 10 ions are precipitated. The
58. The complex ion [Ni(CN)4] is
complex is
(a) square planar and diamagnetic
(a) [Co(H2O)6]CI3 (b) [Co(H2O)5CI]CI2 • H2O
(a) tetrahedral and paramagnetic
(c) [Co(H2O)4CI2]CI • 2H20 (d) [Co(H2O)3CI3] • 3H2O
(a) square planar and paramagnetic (J.E.E. Main, 2017)
(a) tetrahedral and diamagnetic. (I.S.C., 2016) 69. Consider the following reaction and statements :
59. The number of geometric isomers that can exist for square
planar [Pt (Cl) (py) (NH3) (NH20H)]+ is (py = pyridine) [Co(NH3)4Br2] + Br ----- > [Co(NH3)3Br3] + NH3

(a) 2 (b) 3 (I) Two isomers are produced if the reactant complex ion is
(c) 4 (d) 6 (J.E.E. Main, 2015) a cis-isomer.
60. Which of the following compounds is not coloured yellow ? (II) Two isomers are produced if the reactant complex ion is
(a) Zn2[Fe(CN)6] (b) K3[Co(NO2)6] a trans-isomer.
(c) (NH4)3 [As(Mo3O10)4] (d) BaCrO4 (III) Only one isomer is produced if the reactant complex ion
(J.E.E. Main, 2015) is a trans-isomer.
61. The pair having the same magnetic moment is (IV) Only one isomer is produced if the reactant complex ions
[At. No. : Cr = 24, Mn = 25, Fe = 26, Co = 27] is a cis-isomer.
(a) [Cr(H2O)6]2 + and [CoCI4]2" The correct statements are :
(b) [Cr(H2O)6]2+ and [Fe(H2O)6]2+ (a) (I) and (II) (b) (I) and (III)
(c) [Mn(H2O)6]2+ and [Cr(H2O)6]2+ (c) (III) and (IV) (d) (II) and (IV)
(d) [CoCI4]2- and [Fe(H2O)6]2+ (J.E.E. Main, 2016) (I.I.T., J.E.E. 2018)
 Nootan ISC Chemistry-XII

70. The type of isomerism shown by the complex [CoC^fen^l is 71. The geometry and magnetic behaviour of the complex
[Ni(CO)4] are
(a) ionization isomerism
(a) square planar geometry and paramagnetic
(b) coordination isomerism
(b) tetrahedral geometry and diamagnetic
(c) geometrical isomerism
(c) square planar geometry and diamagnetic
(d) linkage isomerism (N.E.E.T., 2018)
(d) tetrahedral geometry and paramagnetic (N.E.E.T., 2018)

Answers
1. (d) 2. (a) 3. (a) 4. (0 5. (c) 6. (0 7. (c) 8. (d) 9. (0 10. (a)

11. (d) 12. (d) 13. (b) 14. (b) 15. (b) 16. (b) 17. (a) 18. (c) 19. (b) 20. (0
21. (0 22. (a) 23. (c) 24. (a) 25. (d) 26. (b) 27. (d) 28. (b) 29. (d) 30. (b)
31. (b) 32. (b) 33. (a) 34. (0 35. (a) 36. (a) 37. (d) 38. (a) 39. (d) 40. (a)
41. (a) 42. (a) 43. (d) 44. (d) 45. (b) 46. (d) 47. (a) 48. (a) 49. (b) 50. (b)
51. (b) 52. (d) 53. (a) 54. (b) 55. (b) 56. (c) 57. (b) 58. (a) 59. (b) 60. (a)
61. (b) 62. (b) 63. (b) 64. (0 65. (0 66. (a) 67. (0 68. (b). 69. (b) 70. (0
71. (b)

Hints
26. Higher the number of unpaired electrons in the central 3d 4s 4p
Mn3+ (3tf4) : |U| ? | ? | |~| □ iiii
metal atom, greater is the paramagnetism of the complex.
2_
28. C204 is a bidentate ligand. 3d 4s 4p
Cr3+ (3b3) : | T| T | T | | ~1 □ IIII
29. Cl” is a weak ligand and is unable to pair up 3d electrons
of Ni2+ ion. Therefore, the complex is formed by sp3 hybridisation (CN- ligands are strong and pairup electrons)
_ o_
and acquires a tetrahedral shape. The complex [Co(CN)6] has no unpaired electron and
34. Cyanido complexes are more stable because CN” is a therefore possesses the lowest value of paramagnetic behaviour.
strong ligand and stabilises the complex to a greater extent. It is actually diamagnetic in nature.
35. [Co(NH3)5CI]CI2 [Co (NH3)5CI]2+ + 2CF 43. gs = Jri (n + 2) BM or 2.84= Jn(n + 2)
1 mole 3 moles of ions in water
which gives n= 2.
2AgNO3 + [Co(NH3)5 CI]CI2 —>
In strong ligand field, cr configuration becomes
2 moles 1 mole
m| T | T | | | and there are only two unpaired electrons left.
[Co(NH3)5CI](NO3)2 + 2AgCI(s)
2 moles 2—
2 4. 3 2 45. The formation and geometry of [NiX4] is as follows :
37. [Ni(NH3)fi] is formed by sp d hybridisation because 3d 4s 4p
configuration of Ni2+ is Is2 2s2 2p6 3s2 3p° 3d8 and NH3 is a (a) Ni atom |TT|t4|T4| T I T I ITT] | | | I
weak ligand, i.e., it is unable to pair up d-electrons.
38. Chlorophyll contains magnesium and not calcium.
(b) Ni2+ ion |T4<|T4<|T4<| T | T 11 11 | | |
39. [Co(en)2CI2]+ shows both geometrical as well as optical
isomerism. ,, sp3 hybridisation
40. The number of unpaired electrons possessed by Mn2+,
(c) sp3 hybrid orbitals |T4jT4<|T4-| T | T | | | | | ~|
Co2+ and Fe2+ in the given complexes are respectively 5, 3 and
0. Hence, [MnCI4]2- has the highest and the [Fe(CN)6F the least ofNi2+ion Vacant sp3
hybrid orbitals
magnetic moment.
41. The optical isomers of [Cr2(C2O4)3]3- are as follows (d) sp3 hybrid orbitals |TT|T4|T4<| T | T | |T4<|T4<|T4<|TT|
in [NiX4]2- Four pairs of electrons
Z X-r x U I FM-v i2-• from four X" ligands
(e) Tetrahedral [NiX4] ion :

42. The electronic configurations of the central metal ions

in the given complexes are as follows :
3d 4s 4p
Co3+ (3d6): mimui I ~| □ | I | |

3d_____ 4s 4p The complex is paramagnetic due to the presence of two

Fe3+ (3d5): lUlUItl I ~l □ I I I I
unpaired electrons and has a tetrahedral geometry.
 Coordination Compounds__________________________ 523

46. Both en and C2O2" are bidentate ligands. Therefore, < OH" < C2O2" < H2O < NCS"
coordination number of E in the given complex is 6. The oxidation < CH3CN < NH3 < en < NO2 < CN" < CO.
state of E is +3. Thus, among the ligands present in the given complexes,
47. The arrangement of ligands in the order of increasing CN" is the strongest ligand and causes maximum splitting in the
field strength is called spectrochemical series. The series is as cf-orbitals of the central metal ion. Hence, for [Co(CN)6] , the
follows : magnitude of Ao is the highest.
I" < Br" < S2" < SCN" < CF < NO3 < F"

TRUE OR FALSE’ TYPE QUESTIONS

State whether the following statements are True or False.
1. An aqueous solution of Mohr’s salt gives the test of both Fe2+ 11. Octahedral complexes having monodentate ligands do not
and SO4" ions. exhibit optical isomerism.
2. An aqueous solution of [Cu(NH3)4]S04 gives the test of both 12. The trans form of the complex [Co(en)2CI2]+ is optically
Cu as well as SO4 ions. active.
3. K2 [CuCI4] is an anionic complex. 13. Complexes involving d sp hybridisation are low spin
4. Oxidation number of Ni in [Ni(C0)4] is zero. complexes.
o_
5. EDTA is a chelating ligand. 14. [Fe(CN)6] is diamagnetic in nature.
6. C0CI3 • 3NH3 gives a white precipitate when treated with 2+ 3 2
15. [Fe(H2O)6] involves sp d hybridisation.
silver nitrate.
7. The IUPAC name of the ligand NH3 is amino. 16. [Ni(NH3)4] is square planar.
8. The IUPAC name of the ion [AuCI4]~ is tetrachloridogold (III) 17. The absorption spectra of complexes can be explained on the
ion.
basis of valence bond theory.
9. [PtCI2(NH3)4]Br2 and [PtBr2(NH3)4]CI2 are ionisation
isomers. 18. CN" is a stronger ligand than NH3.
10. [Cr(SCN)(H2O)5]2+ and [Cr(NCS)(H2O)5]2+ are coordination
19. The complex K[Au(CN)2] is used in the electroplating of gold.
isomers.

Answers
1. T 2. F 3. T 4. T 5. T 6. F 7. F 8. F 9. T 10. F
11. T 12. F 13. T 14. F 15. T 16. F 17. F 18. T 19. T.

FILL IN THE BLANKS’ TYPE QUESTIONS o_

1. The total number of ions furnished by K4[Fe(CN)6] in solution 10. The oxidation state of Fe in [Fe(CN)6] is................
is................ 11. The complex [Co(NH3)6]3+ has a ............. geometry and is
2. The electrically charged species formed by the union of a ............. magnetic in nature.
central metal atom or ion with one or more ligands is called 12. The number of unpaired electrons present in [Cr(NH3)6]3+ is

3. The coordination number of platinum in [PtCI4]2" is.............. 13. The complex [Ni(C0)4]° is............. in shape and is...............
4. Ethylenediamine is a............. dentate ligand. magnetic.
5. The IUPAC name of the complex K3[AgF4] is................ 14. Tetracyanocuprate(ll) ion involves............. hybridisation and
6. The isomerism arising due to the interchange of ligands is............. in shape.
between the coordination spheres of positive and negative 15. Greater the basic strength of the ligand, ............. is the
parts is called............. isomerism. stability of the complex.
7. When all the electrons in a complex are paired, it is............. 16. The ligand used in the estimation of the hardness of water
I in nature. is.................
8. Outer orbital complexes involve ............. hybridisation and 17. Vitamin B12 is a complex of................
are............. spin complexes. 18. Cisplatin found useful in the treatment of cancer has the
9. The complexes involving ............. hybridisation are called formula................
inner orbital complexes. They are............. spin complexes.

Ewers
l.five 2. complex ion 3. 4 4. di
5. potassium tetrafluoroargentate (I) 6. coordination 7. diamagnetic
8. sp3d2, high 9. d2sp3, low 10.+3 11. octahedral, dia
0 12. 3 13. tetrahedral,dia 14. dsp , square planar 15. greater
16. EDTA 17. cobalt 18. czs-[PtCI2(NH3)2]
524 Nootan ISC Chemistry-XII I (

ASSERTION-REASON’ TYPE QUESTIONS

The questions given below consist of an Assertion and a Reason. You have to choose the correct answer (a), (b), (c) or (d) according
to the following clue :
(a) If both Assertion and Reason are CORRECT and Reason is the CORRECT explanation of the Assertion.
(b) If both Assertion and Reason are CORRECT but Reason is not the CORRECT explanation of the Assertion.
(c) If Assertion is CORRECT but Reason is INCORRECT.
(d) If Assertion is INCORRECT but Reason is CORRECT.

Assertion Reason
1. Mohr’s salt, FeSO4 • (NH4)2S04 ■ 6H2O is not a coordination The aqueous solution of this salt gives the test of Fe , NH4 and
compound. SO 4 ions.

2. The complexes, [Co(pn)2CI2]+ and [Co(tn)2CI2]+ are ligand isomers. The ligand 1,2-diaminopropane can exist both as
1,2-diaminopropane (pn) and 1, 3-diaminopropane (t„).

3. The tetrahedral complexes can show geometrical isomerism. This is because all the four ligands lie at the same distance from
central metal atom in a tetrahedral geometry.

4. The trans-[CoCI2(en)2]+ is optically inactive. It is symmetrical because it contains a plane of symmetry.

5. The complex [Fe(H2O)6]2+ is paramagnetic in nature. It consists of two unpaired electrons.

Answers
1. (b) 2. (a) 3. (d) 4. (a) 5. (c)

6NCERT TEXT-BOOK'
I Exercises (with Hints and Solutions)
9.1 Explain the bonding in coordination compounds in terms of 9.5 Specify the oxidation numbers of the metals in the
Werner’s postulates. coordination entities :
Hint: See § 9.1.5. (i) [Co(H2O)(CN)(en)2]2+

9.2 FeS04 solution mixed with (NH4)2SO4 solution in 1 : 1 molar (ii) [CoBr2 (en)2]+
ratio gives the test of Fe2+ ion but CuS04 solution mixed with (iii) [PtCI4]2”
aqueous ammonia in 1 : 4 molar ratio does not give the test (iv) K3[Fe(CN)6] I 94
of Cu2 ' ion. Explain, why? (v) [Cr(NH3)3CI3]
Ans. FeSO4 solution mixed with (NH4)2SO4 solution in 1 : 1 Ans. Suppose the oxidation number of the metal present in
ratio forms a double salt, FeSO4 ■ (NH4)2SO4 • 6H2O known the given complex isx. I 9.S
as Mohr's salt. It ionises as follows : (i) x+(0) + (-l) + 2 x (0) = + 2;
FeS04 ■ (NH4)2S04 • 6H2O ----- > x=+3
(ii) x + 2 x (-l) + 2 x (0) = + 1;
Fe2+ + 2NH4 + 2SO4~ + 6H20 .-. x=+3
(iii) x + 4 x (-1) = -2;
Due to the presence of Fe2+ ions in solution, it gives the test x=+2
of Fe2+ ion. (iv) 3 x (+l)+x + 6 x (—1) = 0;
x=+3
When CuS04 solution is mixed with aqueous ammonia in
(V) X + 3x(0) + 3x(-l) = 0;
1 : 4 molar ratio, a complex salt. [Cu(NH3)4]SO4 is obtained. x= + 3 19.10
It ionises in solution as follows. 9.6 Using IUPAC norms write the formulas for the following :
[Cu(NH3)4] S04 ----- > [Cu(NH3)4]2+ + SO2- (i) Tetrahydroxozincate(ll)

The [Cu(NH3)4]2+ ion does not ionise further to give Cu2+ (ii) Potassium tetrachloridopalladate(ll)

ions. Therefore, its solution does not give the test of Cu2+ ion. (iii) Diamminedichloridoplatinum(ll)
(iv) Potassium tetracyanidonickelate(ll)
9.3 Explain with two examples each of the following: coordination
(v) Pentaamminenitrito-O-cobalt(lll)
entity, ligand, coordination number, coordination polyhedron,
(vi) Hexaamminecobalt (III) sulphate
homoleptic and heteroleptic.
(vii) Potassium tri(oxalato) chromate(lll)
Hint: See § 9.1.2.
(viii) Hexaammineplatinum(IV)
9.4 What is meant by unidentate, didentate and ambidentate
ligands? Give two examples for each. (ix) Tetrabromidocuprate(ll)

Hint: See § 9.1.3 [BL (x) Pentaamminenitrito-N-cobalt(lll)

Coordination Compounds______________ 525
Ans.(i) [Zn(OH)4]2-

(ii) K2[PdCI4]
(iii) [Pt(NH3)2CI2]
(iv) K2[Ni(CN)4]
(v) [Co(NH3)5(ONO)]2+

(vi) [Co(NH3)6]2(SO4)3
(vii) K3[Cr(C2O4)3]
(viii) [Pt(NH3)6]4+
(ix) [CuBr4]2"
(x) [Co(NH3)5(NO2)]2+ (i) [CoCI2(en)2r
(ii) [Co(NH3)CI(en)2]2+
9.7 Using IUPAC norms write the systematic names of the
(iii) [Co(NH3)2CI2(en)]+
following :
(i) [Co(NH3)6]CI3
(ii) [Pt(NH3)2CI(NH2CH3)]CI
(iii) [Ti(H2O)6]3+
(iv) [Co(NH3)4CI(NO2)]CI
(v) [Mn(H2O)6]2+
(vi) [NiCI4]2“

(vii) [Ni(NH3)6]CI2
(viii)
[Co(en) 3]3+

(ix) Ni(C0)4]
Ans. (i) Hexaamminecobalt(lll) chloride
(ii) Diamminechlorido (methylamine) platinum(ll) chloride
(iii) Hexaaquatitanium(lll) ion
(iv) Tetraamminechloridonitrito-N-cobalt(lll) chloride
(v) Hexaaquamanganese(ll) ion
(vi) TetrachloridonickelateGI) ion
(vii) Hexaamminenickel(ll) chloride
(viii) Tris (ethane-1, 2-diamine) cobalt(lll) ion
Geometrical isomers
(ix) Tetracarbonylnickel(O). Optical isomers
9.8 List various types of isomerism possible for coordination
9.12 Write all the geometrical isomers of [Pt(NH3)(Br)(CI)(py)] and
compounds, giving an example of each.
how many of these will exhibit optical isomerism?
Hint: See § 9.3.
9.9 How many-geometrical isomers are possible in the following Hint: See Fig. 9.6.

coordination entities?
None of these isomers will show optical isomerism.
(i) [Cr(C2O4)3]3' 9.13 Aqueous copper sulphate solution (blue in colour) gives :

(ii) [Co(NH3)3CI3]
(i) a green precipitate with aqueous potassium fluoride and
Ans. (i) It is a complex of the type [M(AA)3]n± and is unable to (ii) a bright green solution with aqueous potassium chloride.
show geometrical isomerism. Hence, no geometrical isomers Explain these experimental results.

possible. Ans. Aqueous copper sulphate solution exists as

(ii) Two (fac- and mer-). They will have structures similar to [Cu(H20)4]S04 and has blue colour due to the presence of
those shown in Fig. 9.9. [Cu(H2O)4]2+ ions.
5.10 Draw the structures of optical isomer of: (i) When KF is added, the weak H2O ligands are replaced by
(i) [Cr(C2O4)3]3” F~ ligands, thus forming [CuF4]2- ions which form a green
(ii) [PtCI2(en)2]2+ precipitate.
(iii) [Cr(NH3)2CI2(en)]+ [Cu(H2O)4]2+ + 4F“ ----- > [CuF4]2’ + 4H2O
Ans. (i) See Fig. 9.11. Tetraaquacopper (II) Tetrafluoridocuprate (II)
ion ion
(Green precipitate)

(ii) When KCI is added, Cl ligands replacethe weak H2O

ligands forming [CuCI4]2- ion which has bright green colour.

[Cu(H20)4]2+ + 4CI’ ----- > [CuCI4]2" + 4H2O

tetrachloridocuprate (II)
ion
(bright green colour)
 526 Nootan ISC Chemistry-XII

9.14 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 of copper sulphide is
obtained when H2S(g) is passed through this solution?
Ans. On addition of aqueous KCN to an aqueous solution
of copper sulphate, the coordination entity [Cu(CN)4]
formed as shown below.
get paired up in the presence of weak H2O ligands. The
unpaired electrons undergo d-d transition due to sunlight.
The transition absorbs red light. Therefore, the complex entity
shows complimentary green colour.
In [Ni(CN)4]2-, nickel again exists as Ni24- with 3d8
is configuration and has two unpaired electrons. But in the
presence of strong CN- ligands, these electrons get paired

[Cu(H2O)4]2+ +4CN“ ----- > [Cu(CN)4]2- +4H2O up. In the absence of any unpaired electron, no d-d transition

(Coordination entity is induced. Consequently the complex entity is colourless.

in aqueous 9.21 [Fe(CN)6]4~ and [Fe(H2O)6]2" are of different colours in
copper sulphate solution)
o_ dilute solutions. Why?
The complex entity [Cu(CN)4] thus formed is highly stable Ans. The oxidation state of Fe in both the complexes is +2.
because CN- is a strong ligand. Therefore, on passing H2S(g) Fe2+ has configuration 3d6 and has four unpa.red electrons. In
through its solution, no precipitate of CuS is obtained because [FefCN)^]4-, the CN~ ligands present are strong and pair up
free Cu2+ ions are not available. electrons. On the other hand, in [Fe(H20)6]2 ", the H20 ligands
9.15 Discuss the nature of bonding in the following coordination present are weak and are unable to pair up electrons. Hence,
entities on the basis of valence bond theory : due to a difference in the number of unpaired electrons, these
(i) [Fe(CN)6]4- complexes show different colours in dilute solutions.
(ii) [FeF6]3~ 9.22 Discuss the nature of bonding in metal carbonyls.
(iii) [Co(C2O4)3]3~ Hint: See § 9.7.
(iv) [CoF6]3’ 9.23 Give the oxidation state, d-orbital occupation and coordination
Hint: number of the central metal ion in the following complexes :
(i) d sp , octahedral, diamagnetic (i) K3[(Co(C2O4)3)] (ii) c/s-[Cr(en)2CI2]CI
o o
(ii) sp d , octahedral, paramagnetic (iii) (NH4)2[CoF4] (iv) [Mn(H20)6]S04
2 3
(iii) d sp , octahedral, diamagnetic Ans.
o o
(iv) sp d , octahedral, paramagnetic. Cental
Oxidation Coordination (/-orbital
For details, see § 9.4.1 [BL Complex metal
state number occupation
ion
9.16 Draw figure to show the splitting of o'-orbitals in octahedral
crystal field. (i) K3[Co(C2O4)3] 3 x (+1) +x 6 (C2O42 is Co3+ 3d6, tfe°g
Hint: See Fig. 9.25. + 3 x (-2) didentate)
= 0
9.17 What is spectrochemical series? Explain the difference
x = +3
between a weak field ligand and a strong field ligand. Cr3+
(ii) c/s-[Cr(en)2CI2]CI x + 2 x (0) 6 (en is 3d3, t23
Ans. The arrangement of ligands in the increasing order + 3 x (- 1) didentate)
of their field strength is called spectrochemical series. The = 0
ligands which cause less splitting of o<-orbitals of central x-+ 3
metal atom or ion are called weak field ligands. For such 2 x (+1) +x Co2+ 3d7,e/t23e
(iii) (NH4)2[CoF4] 4
ligands, the value of CFSE (A or 10 Dq) is quite small. On the + 4 x(-1)
other hand, the ligands which cause much larger splitting of =0
(d-orbitals are called strong field ligands. For such ligands, the .-. x = +2
value of A or 10 Dq is much higher. (iv) [Mn(H2O)g]SO4 x + 6 x (0) 6 Mn2+ 3c/ , t2gSg
9.18 What is crystal field splitting energy? How does the -2 = 0
magnitude of Ao decide the actual configuration of d-orbitals .-. x=+2
in a coordination entity?
Hint: See § 9.4.2 [A], [B] (Filling of electrons in d-orbitals). 9.24 Write down the I UPACnamefor each of thefollowingcomplexes

9.19 [Cr(NH3)6]3+ is paramagnetic while [Ni(CN)4]2“ is and indicate the oxidation state, electronic configuration and
coordination number. Also give stereochemistry and magnetic
diamagnetic. Explain, why?
moment of the complex :
Hint: See § 9.4.1 [B] 1 (octahedral complexes)(iv) and
§ 9.4.1 [B] 3 (square planar complexes)(i). (i) K[Cr(H20)2(0204)2] • 3H2O
(ii) [Co(NH3)5CI]CI2
9.20 A solution of [Ni(H20)6] is green but a solution of
[Ni(CN)4]2- is colourless. Explain. (iii) CrCI3(py)3
Ans. In [Ni(H2O)g]2+ nickel exists as Ni2+ with 3d8 (iv) Cs[FeCI4]
configuration. It has two unpaired electrons which do not (v) K4[Mn(CN)6]
Coordination Compounds 527
Ans.

Value of n and magnetic

Oxidation state of Coordina­ Stereo­ Central metal Electronic moment
IUPAC name of the complex
central metal tion number chemistry ion configuration Ps = a/c?(/7 + 2)

Cr3+ OzV3 x 3 .0 n = 3,
(i) Potassium + 1 +x + 2x(0) 6 Octahedral 3c/ , ttgCg
diaquadioxalatochromate + 2 x (-2) = 0 73(3 + 2)
(III) hydrate x=+3
= 3.87 BM
Co3+ 3d , t2geg n = 0,
(ii) Pentaamminechl- x + 5 x (0) + 6 Octahedral
oridocobalt (III) 3 x(-l)=0 70(0 + 2)
chloride .'. x = + 3
= 0 BM

x + 3 x (-1) + Cr3+ 3cr , t2g6g n = 3,

(iii) Trichloridotripyridine 6 Octahedral
chromium (III) 3 x (0) = 0 73(3 + 2)
:. x - + 3 = 3.87 BM
Fe3+ q >-.2x3
(iv) Caesium tetrachlorido + 1 +x + 4 x (-1) 4 Tetrahedral 3c/ , eg t2g n = 5,
ferrate (III) =0 75(5 + 2)
.-. x = + 3
= 5.92 BM

(v) Potassium (+1) x4+x + 6 Octahedral Mn2+ 3d5. t25ge° n = 1,

hexacyanidomanganate 6 x(-l) = 0 7K1 + 2)
(II) X
.-. x = +2
= 1.73 BM

9.25 What is meant by stability of a coordination compound Ans. (ii). [Fe(H2O)6]2+ has the highest magnetic moment.
in solution? State the factors which govern stability of (This is because in (i) Cr3+ has 3 unpaired electrons, whereas
complexes. in (iii) Zn2+ has no unpaired electron. Fe2+ in (ii) has 4
Hint: See § 9.5. unpaired electrons).
9.26 What is meant by the chelate effect? Give an example. 9.30 The oxidation number of cobalt in K[Co(CO)4)] is
Ans. When a polydentate ligand attaches itself to a central (i) + 1 (ii) + 3
metal ion through two or more donor atoms in such a way (iii)-l (iv) - 3
that it forms a five or six membered ring with the central
ion, the effect is called chelate effect. Chelates stabilise a Ans. (iii) -1.
complex. For example, [+1 + x + 4 x (0) = 0, x =- 1]
H2C^H2N> NH2—CH2']2+ 9.31 Amongst the following, the most stable complex is
(i) [Fe(H2O)6]3+ (ii) [Fe(NH3)6]3+
(iii) [Fe(C2O4)3]3" (iv) [FeCI5]3'
h2o—h2n nh^-ch2
Ans. (iii) [Fe(C2O4)3]3-
i.e., [Cu(en)2]2+
(C2O24 is a chelating ligand and stabilises the complex).
9.27 Discuss briefly giving an example in each case the role of
coordination compounds in : 9.32 What will be the correct order for the wavelengths of

(i) biological systems (ii) medicinal chemistry absorption in the visible region for the following :
[Ni(N02)6]4~, [Ni(NH3)6]2+, [Ni(H2O)6]2+?
(iii) analytical chemistry and
(iv) extraction/metallurgy of metals. Ans. The order of ligands present in the given complexes in
Hint: See § 9.6. the spectrochemical series is as follows :
9.28 How many ions are produced from the complex Co(NH3)6CI2 H2O < NH3 < NO2
in solution? Hence, the wavelengths of the light observed will be in the
K (i) 6 (ii) 4
order
(iii) 3 (iv) 2 [Ni(H20)6]2+ < [Ni(NH3)6]2+ < [Ni(N02)6]4-
Ans. (iii) 3 ions are produced. Since the wavelength observed is complementary to that
[Co(NH3)6]CI2 ----- > [Co(NH3)6]2+ + 2CF 7 he
absorbed, the wavelengths of the light absorbed E = —
k A 7
9.29 Amongst the following ions which one has the highest
magnetic moment value? will be in the opposite order, i.e.,
[Ni(NO2)6]4” < [Ni(NH3)6]2+ < [Ni(H2O)6]2+.
(i) [Cr(H2O)6]^ (ii) [Fe(H2O)6]2+ (iii) [Zn(H2O)6]2+
528 Nootan ISC Chemistry-XII

QUESTIONS from isc examination papers

1. Correct the following statement by changing the underlined 7. Write the IUPAC names of the following coordination
part of the sentence. compounds :
In a coordination complex, donation of electron pair takes
(a) [Cr(NH3)4(H2O)2]CI3 (b) [PtCI2(NH3)4][PtCI4]
place from the central metal atom to the ligands. (2009)
(2015)
2. Name the type of isomerism shown by the following pairs of o
coordination compounds : 8. State the hybridization and magnetic property of [Fe(CN)6]

(a) [Co(NH3)5NO2]CI2 and [Co(NH3)5ONO]CI2. ion according to the valence bond theory. (2015)

(b) [Cr(H2O)5CI]CI2 • H2O and [Cr(H2O)4CI2]CI • 2H2O. (2009) 9. What type of isomers are [Co(NH3)5Br]SO4 and
[Co(NH3)5SO4]Br? Give a chemical test to distinguish
3. (a) Give the IUPAC names for the following :
between them. (2015)
(i) Na3[AIF6] (ii) [Co(NH3)5]CI3
10. Write the structures of optical isomers of the complex ion
(b) For the complex ion, [Fe(CN)6] :
[Co(en)2CI2]+. (2015)
(i) Show the hybridisation diagrammatically.
11. (a) Write the IUPAC names of the following :
(ii) Is it an inner orbital complex or an outer orbital complex?
(i) [Co(NH3)4SO4]NO3
(iii) State its magenetic property. (2011)
(ii) K[Pt(NH3)CI3]
4. (a) Write the formulae of the following coordination
compounds : (b) What type of isomerism is exhibited by the following pairs
of compounds :
(i) potassium tetracyanidonickel (0)
(i) [PtCI2(NH3)4]Br2 and [PtBr2(NH3)4]CI2,
(ii) triamminetrinitrocobalt (III)
(ii) [Cr(SCN)(H2O)5]2+ and [Cr(NCS)(H2O)5]2+?
(b) [CoF6] is a coordination complex ion.
(i) What is the oxidation number of cobalt in the complex? (c) How does K2[PtCI4] get ionised when dissolved in water?
(ii) How many unpaired electrons are there in the Will it form precipitate when AgNO3 solution is added to
complex? it? Give a reason for your answer. (2016)

(iii) State the magnetic behaviour of the complex. 12. (a) Write the formula of the following compounds :

(iv) Give the IUPAC name of the complex.
(c) Draw the structural isomer of [Co(NH3)5NO2]CI2 and
name the type of isomerism.
5. (a) (i) State the geometry and magnetic
tetracarbonyl nickel according to the valence bond
theory.
(ii) What type of structural isomers
[Pt(OH^(NH3)4]SO4 and [PtSO4(NH3)4](OH)2? How
will you identify the isomers with a chemical test?
(b) Name the coordination compound used for the following :
(i) Treatment of cancer.
(ii) Treatment of lead poisoning. (Sample Paper, 2013)
6. (a) Write the formula of the following compounds :
(i) Triamminetriaquachromium (III) chloride
(ii) Potassium hexacyanidoferrate (III)
(b) Name the types of isomerism shown by the following
pairs of compounds :
(i) [CoCI(H2O)(NH3)4]CI2 and [CoCI2(NH3)4]CI • H2O
(ii) [Pt(NH3)4][PtCI6] and [Pt(NH3)4CI2][PtCI4]
(c) For the complex ion of [Co(NH3)6]3+:
(i) State the hybridisation of the complex.
(ii) State the magnetic nature of the complex.
(i) Potassium trioxalatoaluminate (III)
(ii) Hexaaquairon(ll) sulphate.
(2012) (b) Name the types of isomerism shown by the following
pairs of compounds :
property of
(i) [Cu(NH3)4] [PtCI4] and [Pt(NH3)4][CuCI4]
(ii) [Co(Pn)2CI2]+ and [Co(tn)2CI2]+
(c) For the coordination complex ion [Co(NH3)6]3+:
are
(i) Give the IUPAC name of the complex ion.
(ii) What is the oxidation number of cobalt in the complex
ion?
(iii) State the type of hybridisation of the complex ion.
(iv) State the magnetic behaviour of the complex ion.
(2017)
13. What type of isomerism is shown by the following coordination
compounds :
[Pt Cl2 (NH3)4] Br2 and [Pt Br2 (NH3)4] Cl2.
Write their IUPAC names. (2018)
14. For the complex ion [Fe(CN)6]3-, state :
(a) the type of hybridisation.
(b) the magnetic behaviour.
(c) the oxidation number of the central metal atom. (2018)
15. Write the IUPAC name of [Co(en)2CI2]+ ion and draw the
(2014) structures of its geometrical isomers. (2018)
ee#