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INDIA’S FIRST NOTES WITH MOST
IMPORTANT SUBTOPICS MARKED
ACCORDING TO JEE MAINS
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SAMPLE PROBLEMS FOR

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UNDERSTANDING WHICH ARE

HIGHLY EXPECTED IN JEE MAINS
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EXAM
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 Chapter - 4
COORDINATION COMPOUNDS AND
ORGANOMETALLICS
Introduction
The coordination compounds contain a central metal atom or ion of Transition metals (d-block elements)
surrounded by a number of oppositively charged ions or neutral molecules (called as Ligands) with more than
its normal valency. These are formed from apparently saturated molecules capable of independent existence.
For example, when aqueous ammonia is added to green solution of nickel chloride, (NiCl2), the colour changes
to purple. The Ni 2+ ions almost disappear from the solution of nickel chloride,
The solution, on evaporation, yields purple crystals corresponding to the formula [Ni(NH3)6]Cl2.

NiCl2 + 6NH3 [ Ni ( NH 3 ) 6 ]Cl 2

Coordinati on compound
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Such a compound is called coordination (or complex) compound. The properties of the complex compound
are completely different from those of Ni2+ ions or ammonia molecules.
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When the compound is dissolved in water, there is hardly any evidence of Ni2+ ions or ammonia molecule. It
ionises to give a new species [Ni(NH3)6]2+. Such an ion is called complex ion.

[Ni(NH3)6]Cl [ Ni( NH 3 ) 6 ]2 + 2Cl–

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Complex ion

At this stage, it may be noted that the species in the square brackets does not ionise. It remains as
single entity.
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Differences between Coordination Compounds and Double Salts

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The coordination compounds are different from double salts. Double salts are addition or molecular compounds
which are formed by two apparently saturated compounds but they lose their identity when dissolved in
water. The common double salts are :

Mohr's salt FeSO4. (NH4)2SO4. 6H2O

Potash alum K2SO4. Al2(SO4)3.24H2O

For example, Mohr's salt dissolves in water and gives the characteristic properties of Fe2+, NH4+ and SO42–
ions. Thus, double salts are stable in solid state but break up completely into its constituents when dissolved
in water

2+ + 2–
FeSO4.(NH4)2SO4 water
 Fe (aq) + 2NH4 (aq) + 2SO4 (aq)

On the other hand, the coordination, compounds retain their identities in the solid state as well as when
dissolved in water or any other solvent. Their properties are completely different from the constituents
(metal ions or molecules). For example, [Ni(NH3)6]Cl2 does not show the properties of Ni or ammonia.

[ 165 ]
Coordination Compounds and Organometallics

4.1 Important Terms used in Coordination Compound

1. Ligands and central metal atom/ion: In the formation bonds, the anions or the neutral
molecules act as the electron pair donors whereas the metal atom or ion acts as the electron
pair acceptor.

The donor atoms, molecules or anions which donate a pair of electrons to the metal atom or
ion and form a coordinate bond with it are called ligands. The metal atom or ion to which
these ligands are attached is called central metal atom or ion.

Classification of Ligands: There are two ways ligands can be classified.

(a) Classification based on donor and acceptor properties of the ligands.

Ligands having one or more lone pair(s) of electrons are further classified as:
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(i) Ligands containing vacant -type orbitals can receive backs donated  electrons from
the metal ion in low oxidation state. For example CO, NO, CN– and unsaturated
organic molecules.
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Such ligands, have filled donor orbitals in addition to  acceptor orbital. This in the
complex formed by such ligands both metal and the ligand act as donor and acceptor
π
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M σ
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(ii) Ligands which have no vacant orbital to get back donated electrons from the metal
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e.g. H2O, NH3, F–, etc.

(b) Ligands having no lone pair of electrons but -bonding electrons

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e.g., C2H4, C6H6, C5H9.

Classification based on the number of donor atom present in the ligands.

Monodentate or unidentate ligands. The ligands that can coordinate to the central metal ion
at one site only are called monodentate. Such ligands may be neutral molecules, negatively
or positively charge.

F–, Cl–, CN–, OCN–, H2O, NH3, NO 2 , NO+, NH2– NH 3

A monodentate ligand having more than one lone pair of electrons may simultaneously
co-ordinate with two or more atoms and this act as bridge between the metal ion, in such a
case, of is called a bridging ligand and the complex thus formed is known as bridged complex.

e.g., OH–, F–, NH 2 , CO, O2–, SO24 .

[ 166 ]
Coordination Compounds and Organometallics

Typical ligands meet within coordination compounds

Ligand Charge Type

H2O 0 Unidentate

NH3 0 Unidentate

CO 0 Unidentate

H2C NH2
ethylenediamine (en)
(or ethane-1,2-diamine) 0 Didentate
H2C NH2

Cl–, Br–, I–CH3COO–, CN–, SCN– –1 Monodentate

NH2
H2C glycinate ion (gly)
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–1 Didentate
COO

COO
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(oxalate ion) –2 Didentate

COO
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CH3 COO
H2C N
CH3 COO
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CH3 COO
–4 Hexadentate
H2C N
CH3 COO
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(ethylenediaminetetracetate ion, (i.e. edta)–1

Ambidentate ligands: Unidentate ligands containing more than one coordinating atoms are
called ambidentate ligands.

Example: NO2, ONO, SCN, NCS, CN, NC.

2. Coordination Number: The total number of unidentate ligands (and double the number of
didentate ligands if any) attached to the central metal ion through coordinate bonds is called
the coordination number.

3. Coordination sphere or coordination entity and Counter ions: The central atom and the
ligands which are directly attached to it are enclosed in square brackets and are collectively
termed as the coordination sphere or coordination entity.

[ 167 ]
Coordination Compounds and Organometallics

4. Coordination Polyhedron: The spatial arrangement of the ligand atoms which are directly
attached to the central atom / ion is called coordination polyhedron around the central
atom/ion.

Example: Tetrahedral, Square planar, Octahedral, Square pyramidal, Trigonal bipyramidal.

5. Oxidation Number or Oxidation State: The oxidation number of the central atom is defined
as the charge that it carries as calculated by assigning appropriate charges to the ligands and
equating the sum of the charges on the central atom and the ligands equal to the charge on
the coordination sphere.

6. Charge on the Complex Ion: The charge carried by a complex ion is the algebraic sum
of the charges carried by central metal ion and the ligands coordinated to the central metal
ion.

7. Homoleptic and Heteroleptic complexes: Complexes in which the metal atom or ion is
linked to only one type of ligands are called homoleptic complexes, e.g.., [Co(NH3)6[2+. The
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complexes in which the metal atom or ion is linked to more that one kind of ligands are called
heteroleptic complexes, e.g., [Co(NH3)4Cl2]+.
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8. Homonuclear and Polynuclear complexes: Complexes in which only one metal atom is
present are known as homonuclear complexes. All the examples given so far are of the
homonuclear complexes. Complexes in which more than one metal atom is present are known
as polynuclear complexes.
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Example: [Cu(Phen)2]3 [Cr(NCS)6]2.2H2O

9. Effective Atomic Number (EAN): Sidgwick extended the Lewis theory to account for the
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bonding in the coordination compounds. He introduced the term co-ordinate bond for a shared
electron pair if it initially belonged to one atom (donor atom) only. In this case, the donor atom
acts as a lewis base and the metal ion acts as a Lewis acid. The metal on accepts the electron
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pairs till it achieves the next inert gas configuration. This is called the effective number rule.

The total number of electrons, which the central metal atom appears to possess in the complex,
including those gained by it in bonding, is called effective atomic number of central metal ion.
When the EAN was 36 (Kr), 54 (Xe) or 86 (Rn), the EAN rule was said to be followed.

For example, [Co(NH3)6]3+ cobalt has an atomic nimbler 27. In Co3+ number of electrons is
24. Each ammonia molecule donates a pair of electrons. So, EAN becomes
24 + (2 × 6) = 36.

In many cases it was found EAN in a complex should be equal to number of electrons present
in next noble gas.

There are exceptions as well For example,

EAN of [Ni(NH3)6]2+ is 38 and [Cr(NH3)6]3+ is 33.

[ 168 ]
Coordination Compounds and Organometallics

The EAN of metals in some metal complexes

Metal complex Atomic number Electrons Electrons EAN

of metal with metal donated by the
ion ligands to metal ion

[Co(NO2)6]3– Co (27) 24 6 × 2 = 12 24 + 12 = 36

[Cd(NH3)4]2+ Cd (48) 46 4×2=8 48 +8 = 54

[Pt(Cl6]2+ Pt (78) 74 6 × 2 = 12 74 + 12 = 86

[Cr(CO)6] Cr (24) 24 6 × 2 = 12 24 + 12 = 36

[Ni(CO)4] Ni (28) 28 4×2=8 28 + 8 = 36

[Ag(NH3)2]Cl Ag (47) 46 2×2=4 46 + 4 = 50

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K4[Fe(CN)4] Fe (26) 24 6 × 2 = 12 24 + 12 = 36

[Cu(NH3)4]SO4 Cu (29) 27 4×2=8 27 + 8 = 35

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K1[Ni(CN)4] Ni (28) 26 4×2=8 26 + 8 = 34

K2[PtCl6] Pt (78) 74 6 × 2 = 12 74 + 12 = 86

K3[Cr(C2O4)3] Cr (24) 21 6 × 2 = 12 21 + 12 = 33
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K3[HgI4] Hg (80) 78 4×2=8 78 + 8 = 86

Illustration 1: What is the coordination number of Fe in [Fe(EDTA)]?

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Solution: (6) As (ETDA)4– has coordination 6.

Illustration 2: What is oxidation state and coordination number of central metal ion in [CoF4]2–?
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Solution: [CoF4 ]2 x + (–4) = –2 or x = +2, Coordination ion = 4 as F – is monodentate and its

number is 4.

Illustration 3: Give one example of a biodentate ligand.

H2C NH2
Solution: Ethylene diamine, (en) is bidentate ligand.
H2C NH2

Illustration 4: What are ambidentate ligands? Give some example

Solution: Unidentate ligands continuing more than one coordinating atoms are called ambidentate
ligands.

Example: NO2, ONO, SCN, NCS, CN, NC.

[ 169 ]
Coordination Compounds and Organometallics

Illustration 5: Given an example of a hexadentate ligand.

Solution: EDTA (ethylenediaminetetraceate ion)

CH3 COO
H2C N
CH3 COO
CH3 COO
H2C N
CH3 COO

SAMPLE PROBLEMS 4.1 (MCQ)

Problem 1: Which one of the following is a tridentate ligand?
(a) NO 2 (b) oxalate ion
(c) Glycinate ion (d) dien
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Solution: (d) Diethylenetriamine is tridentate (Dien) is tridentate.

Problem 2: An example of ambidentate ligand is

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(a) Ammine (b) Aquo

(c) Oxalato (d) Thiacyanato

Solution: (d) SCN is ambidentate

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Problem 3: In the complex [Pb(O2) (en)2Br]2+, coordination number and oxidation number of platinum
are:
(a) 4, 6 (b) 6, 4
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(c) 4, 4 (d) 5, 4

Solution: (b) O2 and Br– is monodentate while en is bidentate.

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Problem 4: Which ligand is useful for removal of the toxic effect of lead metal from the body in chelate
therapy treatment?

COO
(a)
COO

(b) CH3COO–
OOCH2 C CH2 COO
N CH2 CH2 N
(c)
OOCH2 C CH2 COO

(d) AsO34

Solution: (c) Act like leaching agent.

[ 170 ]
Coordination Compounds and Organometallics

Problem 5: A chelating agent has two or more than two donor atoms to bind to a single metal ion. Which
of the following is not a chelating agent?
(a) thiosulphato (b) Oxalato
(c) gycinato (d) ethane-1,2-diamine

Solution: (a) Thiosulphate is monodentate.

Problem 6: Which of the following species is not expected to be a ligand?

(a) NO (b) NH 4
(c) NH2CH2CH2NH2 (d) CO

Solution: (b) NH 4 does not have lone pair electron to donate. So cannot act as ligand.

Problem 7: Identify the correct statement for the behaviour of ethane-1,2-diamine as a ligand
(a) It is a neutral ligand (b) It is a didentate ligand
(c) It is a chelating ligand (d) All of these
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Solution: (d) Self explanatory

Problem 8: Which of the following complexes are homoleptic?

(a) [Co(NH 3)6]3+ (b) [Co(NH3)4Cl2]+
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(c) [Ni(CN)4]2– (d) Both (a) and (c)

Solution: (d) Self explanatory

Problem 9: Oxidation number and coordination number of silver in Tollen’s reagent respectively are
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(a) 1, 1 (b) 2, 1
(c) 2, 2 (d) 1, 2

Solution: (d) [Ag(NH3)2]OH is Tollen’s reagent.

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Problem 10: The ligand NH2 – NH 3

(a) tridentate (b) pentadentate
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(c) monodentate (d) bidentate

Solution: (c) Self explanatory

4.2 Nomenclature of Coordination Compounds

The nomenclature system given by IUPAC is as given below :

1. Order of naming ions. In ionic complexes, the cation is named first and then the anion (as in
NaCl: sodium chloride).
Non-ionic complexes are given a one word name.

2. Naming the coordination sphere. In naming the coordination sphere, the ligands are named
first and then the central metal ion.

3. Name of ligands. The names of negative ligands end in -o and names of positive ligands end in
-ium. The neutral ligands are named as such. For example :

[ 171 ]
Coordination Compounds and Organometallics

(i) negative ligands end in -o :

F– fluorido
–
Cl chlorido NO 2 – nitrito-N
ONO – nitrito-O
Br – bromido SO 4 2– sulphato
– –
OH hydroxido COO Oxalate

CN – cyanido COO–

CH3 COO – acetato

SCN– thiocyanato O 2– oxo
2– –
O2 peroxo N3 azido
– –
NCS isothiocyanato H hydrido
2– –
CO 3 carbonato NO 3 nitrato
NH 2 – amido NH 2 – imido
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ClO3 – chlorato S 2 O 3 2– bisulphato

(ii) positive ligands end in -ium

NO + nitrosonium NH 2 NH 3 + hydrazinium
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NO 2 + nitronium

(iii) neutral ligands are named as such

NH 2CH 2CH 2NH 2 ethylenediamine

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C 6 H5 N pyridine
(C 6 H5 )3 P triphenylphosphine

However, there are a few exceptions in naming ligands. For example,

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H2 O aquo/aqua NH 3 ammine
NO nitrosyl CO carbonyl
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H2O is also named 'aqua' these days.

4. Order of naming ligands. When more than one type of ligands are present, (for Heteroleptic
complex) they are named in alphabetical order of preference without separation by hyphen.
For example, in the complex [Co(NH 3)4 Cl(NO2)]+, the ligands are named in the order :
ammine, chlorido and nitro. Similarly, in the complex K3[Fe(CN)5NO], the ligands are named
as cyanido and nitrosyl.

5. Ending of names. When the complex is anionic, the name of the central metal atom ends
in -ate. For cationic complex [Co(NH3)6] Cl3 is named without characteristic ending of the
name of the metal as :

[Co(NH3)6]Cl3 Hexaamminecobalt (III) chloride

The coordination compound, K[Pt(NH3)Cl5] which contains the anionic complex [Pt(NH3)Cl5]–
is named with ending of the name of the metal as -ate.

[ 172 ]
Coordination Compounds and Organometallics

K[Pt(NH3)Cl5] Potassium amminepentachloroplatinate (IV)

Similarly, the anionic complex Ca2[Fe(CN)6] is named as calcium hexacyanoferrate (II).

It may be noted that for anionic complexes the Latin names of certain metals are commonly
used. For example,

ferrate for Fe, cuperate for Cu argentate for Ag,

aurate for Au stannate for Sn, etc.

However, if the complex is cationic the name of the metal is given as such, e.g. iron for Fe,
silver for Ag, gold for Au, copper for Cu, etc. For example,

K3[Fe(CN)6] : Potassium hexacyanoferrate (III)

[Fe(CO)5] : Pentacarbonyl iron (0)

6. Bridging groups in bidentate ligands. For ligands which act as bridge between two metal
atoms, the Greek letter () is written before their names. For example,
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NH2
(NH3)4 Co Co (NH3)4 (NO3)4
NO2
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In this case, the ligands are NH2– (amido), NO2– (nitro) and NH3 (ammine). The oxidation
state of cobalt is +3 as Tetramine cobalt (III) -amido--nitrotetraamine cobalt (III)
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OH
(H2O)3Fe — NH2 — Fe(H2O)3
PO4
OH
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In this case the name is Bis triaqua ––amido–, µ-dihydroxodiiron(III)phosphate

7. Point of attachment. When a ligand can coordinate through more than one atom, then the
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point of attachment of the ligand is indicated by putting the symbol of the atom through which
coordination occurs after the name of the ligand. Sometimes, different names are used for
alternative modes of attachment. For example,

–NO2– (through N) : nitro, –ONO– (through O) : nitrite ;

–SCN– (through S) : thiocyanato ; –NCS– (through N) : isothiocyanoto

For example,

[Co(NH3)3(NO2)3] Triamminetrinitrocobalt (III)

[Co(NH3)5(ONO)] SO4 Pentaamminenitritocobalt (III) sulphate

Illustration 1: Formulate the compound tetraammineaquachloridocobalt(III) chloride.

Solution: Anion (simple ion) = Cl– for the coordination entity, writing first the symbol for metal atom
and then the ligands in the alphabetical order, we have

[ 173 ]
Coordination Compounds and Organometallics

Cation (complex ion) = [Co(NH3)4 (H2O)Cl]x where x is the charge on the complex ion
x = oxidation state of cobalt + charge on the ligands
x =+3 + 0 + 0 + (–1) = + 2
(H2O and NH3 are neutral groups and carry no charge. Only chlorido group carries
charge = –1
Charge on one anion = –1
Charge on complex cation =+2
Clearly, two anions will neutralise the charge of the cation
Hence, formula of the given compound is [Co(NH3)4(H2O)Cl]Cl2

Illustration 2: Write the formulae of the following coordination compounds:

(i) Sodium pentacyanonitroxylsulphidoferrate (III)
(ii) Potassium tetrahydroxozincate (II)

Solution: (i) Cation (simple ion) = Na+

For the coordination entity, writing first the symbol for metal atom and then the ligands
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in the alphabetical order, we have

Anion (complex ion) = [Fe(CN)5(NO)s]x
x = +3 + (–5) + (0) + (–2) = –4, i.e., Charge on anion = –4
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Charge on one cation (Na+) = +1

Balancing the positive and negative charges, the formula of the compound will be
Na 4[Fe(CN)5(NO)S]

(ii) Cation = K+
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Anion (complex ion) = [Zn(OH)4]x

x = + 2 + (–4) = –2, i.e., Charge on the anion = –2
Charge on one cation (K+) = + 1
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Balancing the positive and negative charges, the formula of the compound will be
K2[Zn(OH)4].
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Illustration 3: Write down the formula of the following coordination compounds:

(i) hexaaquairon (II) sulphate
(ii) potassium tetracyanonickelate (III)
(iii) chloronitrodiammineplatinum (II)

Solution: (i) [Fe(H2O)6]SO4

(ii) K3[Fe(CN)6
(iii) K2[Co(CN)5NO]

SAMPLE PROBLEMS 4.2 (MCQ)

Problem 1: The correct name for the complex K3[Fe(C2O4)3] is:
(a) Potassium ferric oxalate (b) Potassium iron (III) trioxalate
(c) Potassium trioxalato iron (III) (d) Potassium trioxalatoferrate (III)

Solution: (d) Self explanatory

[ 174 ]
Coordination Compounds and Organometallics

Problem 2: The correct formula of the complex tetraammineaquachlorocobalt (III) chloride is

(a) [Cl (H2O) (NH3)4Co] Cl (b) [CoCl (H2O) (NH3)4] Cl
(c) [Co (NH3)4 (H2O) Cl] Cl (d) [CoCl (H2O) (NH3)4] Cl

Solution: (c) Self explanatory

Problem 3: The correct name of the complex ion [Co(en)2Cl(ONO)]+ is

(a) Cobalt diethylene diamine chloronitrate ion.
(b) Chlorodiethyldiaminenitrito cobalt (III) ion.
(c) Chloronitritodiethyldiamine cobalate (III) ion.
(d) Chlorobis(ethylenediamine)nitrito cobalt (III) ion.

Solution: (d) Self explanatory

Problem 4: The correct name for the complex [Cr(NH3)6] [Co(C2O4)3] is

(a) Hexaamminechromium (III) trioxalatocobalt (III)
(b) Hexaamminechromate (III) trioxalatocobalate (III)
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(c) Hexaamminechromium (III) trioxalatocobaltate (III)

(d) Hexaamminechromate (III) trioxalatocobalt (III).
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Solution: (c) Self explanatory

Problem 5: The correct IUPAC name of [Mn3(CO)12] is

(a) Dodecacarbonylmaganate (0) (b) Dodecacarbonylmanganic (II)
(c) Dodecacarbonyl trimanganese (0) (d) Manganicdodecacarbonyl (0)
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Solution: (a) Self explanatory

Problem 6: When 1 mol CrCL36H2O is treated with excess of AgNO3, 3 mol of AgCl are obtained.
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The formula of the complex is

(a) [CrCl3 (H2O)3].3H2 O (b) [CrCl2(H2 O)4]Cl.2H2 O
(c) [CrCl(H2O)5]Cl2H2 O (d) [Cr(H2 O)6]Cl3
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Solution: (d) As 3 moles of HCl is formed so 3 ionisable Cl– ion are present. Which possible from
option (d)

Problem 7: The correct IUPAC name of [Pt(NH3)2Cl] is

(a) Diamminedichloridoplatinum (II) (b) Diamminedichloridoplatinum (IV)
(c) Diamminedichloridoplatinum (0) (d) Dichloridodiammineplatinum (IV)

Solution: (a) Self explanatory

Problem 8: The stabilisation of coordination compounds due to chelation is called the chelate effect.
Which of the following is the most stable complex species?
(a) [Fe(CO)5 ] (b) [Fe(CN)6 ]3–
(c) [Fe(C 2 O4 ) 3] 3– (d) [Fe(H2 O) 6] 3+

Solution: (c) Oxalate is chelating in nature.

[ 175 ]
Coordination Compounds and Organometallics

Problem 9: IUPAC name of sodium cobaltinitrite is

(a) Sodium cobaltinitrite (b) Sodium hexanitritocobaltate (III)
(c) Sodium hexanitrocobalt (III) (d) Sodium hexanitritocobaltate (II)

Solution: (b) Self explanatory

Problem 10: According to IUPAC nomenclature, sodium nitropruside is named as

(a) Sodium nitroferricyanide (b) Sodium nitroferrocyanide
(c) Sodium petacyanonitrosylferrate (II) (d) Sodium pentacyano nitrosylferrate (III)

Solution: (d) Self explanatory

4.3 Isomerism in Coordination Compounds

Two or more compounds having the same molecular formula but different properties are called
isomers and the phenomenon is called isomerism. Isomers can be broadly classified into two major
categories :
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(a) Structural isomerism (b) Stereoisomerism

(a) Structural isomers: The isomers which have same molecular formula but different structural
arrangement of atoms or groups of atoms around the central metal ion are called structural
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isomers. These are discussed below:

1. Ionisation isomerism. The compounds which have same molecular formula but give
different ions in solution are called ionisation isomers. In this type of isomerism, the
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difference arises due to the interchange of groups within or outside the coordination
spheres.

e.g. [Co(NH3)5Br] SO4 [Co(NH3)5Br]2+ + SO42–

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Pentaamminebromido Gives test of SO42– ions

cobalt (III) sulphate
(red-violet)
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[Co(NH3)5SO4]Br [Co(NH3)5SO4]+ + Br–

Pentaamminesulphato Gives test of Br– ions
cobalt (III) bromide
(Red)

2. Hydration isomerism. The compound which have the same molecular formula but differ
in the number of water molecules present as ligands or as molecules of hydration are
called hydrate isomers.

[Cr(H2O)6]Cl3, [Cr(H2O)5Cl] Cl2.H2O and [Cr(H2O)4Cl2]Cl.2H2O

They differ largely from one another in their physical and chemical properties, as illustrated
below:

(i) [Cr(H2O)6]Cl3 It does not lose water when treated with conc. H2SO4
Violet and three chloride ions are precipitated with AgNO3.

[ 176 ]
Coordination Compounds and Organometallics

(ii) [Cr(H2O)5Cl] Cl2.H2O It loses one water molecule when treated with conc.
Blue green H2SO4 and 2Cl– ions precipitated with AgNO3.

(iii) [Cr(H2O)4Cl2]Cl.2H2O It loses two water molecules on treatment with conc.

Green H2SO4 and one Cl– ions precipitated with AgNO3.

3. Coordination isomerism. The type of isomerism occurs in compounds containing both

cationic and anionic complexes and the isomers differ in the distribution of ligands in the
coordination sphere of cationic and anionic parts. The example are :

(i) [Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]

(ii) [Cu(NH3)4][PtCl4 ] and [Pt (NH3)4][CuCl4 ]

4. Linkage isomerism. The compounds which have the same molecular formula but differ
in the mode of attachment of ligand to the metal atom or ion are called linkage isomers.
For example, in NO2– ion, the Nitrogen atoms as well as the Oxygen atom can donate
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their lone pairs. The unidentate ligands which can bind to the central atom through two
donor atoms are also called ambidentate ligands. Other example of ligands are :

NO2– nitrito-N ONO– nitrit – O

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CN cyano (through C) NC isocyano (through N)

SCN thiocyanato (through S) NCS isothiocyanato (through N)

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[Co(NH3)5(NO2)]Cl2 Pentaamminenitrito-N-Cobalt (III) chloride

Yellow brown

[Co(NH3)5 (ONO)]Cl2 Pentaamminenitrito-O-Cobalt (III) chloride

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Red

5. Ligand isomerism: Some ligands themselves are of capable of existing as isomers.

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For example, diaminopropane can exist as 1,2-diaminopropane (pn) and 1,3-

diaminopropane, when these type of lingands are associated to form complexes the
complexane isomers of each other.

Example:

H H H H H H
Co C C C H Cl2 and Co C C C H Cl2 ions
NH2 H NH2 2 H NH2 NH2 2

6. Coordination postion isomerism: In some poly nuclear complexes, interchanges of the

liganoid between the metal atoms which are present as a part of the complex is possible.
This type of interchange of ligands between the metal atoms give rise to coordination
position isomerism for example.

[ 177 ]
Coordination Compounds and Organometallics

2+
NH2

(H3 N)4 Co Co(NH3 )3 Cl 2 Unsymmetrical form

O2

NH2 2+

Cl(NH3 )4 Co Co(NH3 )3 Cl Symmetrical form

O2

7. Polymerisation isomerism: This not the true isomerism because of occurs between
compound having the same emperical formula, but different molecular weight for example,
[Pt(NH3)2Cl2] [Pt(NH3)4], [Pt(Cl4)] [Pt(NH3)Cl3]2 and [Pt(NH3)3Cl]2 [PtCl4] all have the
same emperical formula.

(b) Stereoisomers: Stereoisomers are those isomers which have the same position of atoms
or groups but they differ in the spatial arrangements around the central atom. Stereoisomerism
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involves two types of isomerism viz., geometrical isomerism and optical isomerism. These are
discussed below :

1. Geometrical isomerism. Geometrical isomerism is due to ligands occupying different

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positions around the central ion. The ligands occupy positions either adjacent to one
another or opposite to one another. These are referred to as cis-form (ligands occupy
adjacent positions) and trans-form (ligands occupy opposite positions). This type of
isomerism is, therefore, also referred to as cis-trans isomerism.
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Geometrical isomerism of compounds with coordination numbers 4 and 6 is most important

and is discussed here.
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(i) Geometrical isomerism in complexes of coordination number 4: The complexes

having coordination number 4 adopt tetrahedral or square planar geometry. The geometrical
isomerism is not possible to one another in these complexes. Tetrahedral complexes do
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not show geometrical isomerism this is because all position are adjacent to one another
in this complex. However, square planar complexes show geometrical isomerism.

(a) Square planar complexes of the MA2X2, MA2XY, MABX2, MABXY can exist as
geometrical isomers (Here A and B are neutral ligands such as H2O, NH3, CO, NO,
C5H5N whereas X and Y are anionic ligands such as Cl–, NO2–, CN–, SCN–, etc.

(i) [Pt(NH3)2Cl2] exists in cis and trans forms as :

Cis Trans-
(Pale yellow) [Pt(NH3)2Cl2] (Dark yellow)

[ 178 ]
Coordination Compounds and Organometallics

(ii) [Pt(py)2 (NH3) Cl] exists in cis and trans form as :

Cis- Trans-
(b) The square planar complexes containing unsymmetrical bidentate ligands such as
[M(AB)2] also show geometrical isomerism. For example, the complex, [Pt(gly)2] where
gly = H2NCH2COO– (glycinato) exists in cis and trans forms. Where, as M(AA)2 do not
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Cis- Trans-
It may be noted that the square planar complexes of the type MA4, MA3X or MAX3 will
not show geometrical isomerism because in these cases, the spatial arrangements of the
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complexes are equivalent.

(ii) Geometrical isomerism in complexes with coordination number 6: The complexes
having coordination number 6 adopt octahedral geometry.
(a) The octahedral complex of the type MA4X2, MA2X4, MA3X3, MA4XY etc. exhibit
an

geometrical isomerism. Some common examples are :

(i) An octahedral complex [Co(NH3)4Cl2]+ can exist as cis and trans- isomers :
ka
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Cis-(Violet) [Co(NH3)4 Cl2 ] Trans-(Green)

(ii) [Rh(py)3Cl3 exists as facial and Meridional isomers.

facial meridional

[ 179 ]
Coordination Compounds and Organometallics

(b) Octahedral complexes of the type M(AA)2X2 and M(AA)2XY can also exist as cis
and trans isomers, where AA represents a symmetrical bidentate ligand such as
ethylendiamine (en), oxalate ion (ox) For example, an octahedral complex
[Co(en)2Cl2]+ exists as two isomers.

Cis- [Co(en)2Cl2]+ Trans-

There are very large number of other geometrical isomers known but we have considered
only simple examples.
JE

2. Optical isomerism. There are certain substances which can rotate the plane of polarised
light. These are called optically active substances. The essential condition for a substance
to show optical activity is that the substance should not have a plane of symmetry in its
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structure. The optical isomers have identical physical and chemical properties. They differ
only in the direction in which they rotate the plane of polarised light. The d and l isomers
are mirror images of each other just as left hand is mirror image of the right hand. These
mirror image compounds are non-superimposable on each other and do not possess the
plane of symmetry.
an

The common examples of complexes showing optical isomerism are octahedral complexes
having bidentate ligands. For example,
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(i) Complexes of the type M(AA)3 (where AA is symmetrical bidentate ligand) such as
[Co(en)3]3+ and [Cr(ox)3]3– exist as optical isomers.
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Mirror

[ 180 ]
Coordination Compounds and Organometallics

(ii) Complexes of the type [M(AA)2X2] or [M(AA)2XY] (where AA is symmetrical

bidentate and X and Y are monodentate ligands) also exhibit optical activity. Some
common examples are [Co(en)2Cl2]+, [Rh(en)2Cl2]+, etc. It has already been shown
that complex [Co(en)2Cl2]+ forms geometrical isomers (cis and trans form). It is
interesting to note that the trans form does not show optical isomerism, i.e., it cannot
be resolved into optical isomers. The reason is that the molecule has a plane of
symmetry. On the other hand, the cis-isomer is unsymmetrical and can be resolved
into optical isomers.
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Trans-[Co(en)2Cl2]+ isomer
Superimposable mirror images
(Optically inactive)
ES
an
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Cis-(Co(en)2 Cl2]+ isomers

(Optically active)
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(iii) Complexes of the type [M (AA)X2Y2] containing one symmetrical bidentate ligands
show optical isomerism. For example, [Co(en)(NH3)2Cl2]+ exists in d- and l- forms.

(iv) Octahedral complexes containing hexadentate ligands such as ethylenediaminetetracetato

(EDTA) also show optical isomerism. For example, [Co(EDTA)]– exists as two optical
isomers.

[ 181 ]
Coordination Compounds and Organometallics

SAMPLE PROBLEMS 4.3 (MCQ)

Problem 1: Which of the following is a pair of ionization isomers ?
(a) [Co(NH3)5Br]SO4 and [Co(NH3)5 SO4 ]Br
(b) [Cr(H2O)5Cl]Cl2 .H2O and [Cr(H2O)4.Cl2]Cl.2H2 O
(c) [Co(NH3)6Cr](CN)6 ] and [Cr(NH3)6]Co(CN)6 ]
(d) cis-[Pt(NH3)2Cl2] and trans- [Pt(NH3)2Cl2 ]

Solution: (a) Ionisation isomers gives different ions.

Problem 2: The complex ions [Co(NH3)5(NO2)]2+ and [Co(NH3)5(ONO)]2+ are called

(a) Ionization isomers (b) Linkage isomers
(c) Coordination isomers (d) Geometrical isomers

Solution: (b) When ligands can coordiante with them either of two atoms it give rise to coordination
isomerism.

Problem 3: Which of the following complex or the complex ion will show geometrical isomerism ?
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(a) [Pt(NH3)2Cl2 ] (b) [Pt(NH3 )Cl5 ]–

(c) [Pt(NH3)5Cl]3+ (d) [Co(NH3)6]Cl3

Solution: (a) Self explanatory

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Problem 4: Geometrical isomerism in coordination compounds is exhibited by

(a) square planar and tetrahedral complexes
(b) square planar and octahedral complexes
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(c) tetrahedral and octahedral complexes

(d) square planar, tetrahedral and octahedral complexes

Solution: (b) Tetrahedral complex does not show geometrical isomerism.

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Problem 5: Which of the following complex ions will not show optical activity ?
(a) [Pt(Br)(Cl)(I)(NO2 )(py)NH3 ] (b) cis-[Co(en)2 Cl2]+
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(c) [Co(en)(NH3)2 Cl2 ]+ (d) [Cr(NH3)4Cl2 ]+

Solution: (d) Asymetrical complex show optical isomerism.

Problem 6: Due to the presence of ambidentate ligands coordination compounds show isomerism.
Palladium complexes of the type [Pd(C6H5)2(SCN)2] and [Pd(C6H5(NCS)2]Cl represent
(a) linkage isomers (b) coordination isomers
(c) ionisation isomers (d) geometrical isomers

Solution: (a) When ligands can coordiante with them either of two atoms it give rise to coordination
isomerism.

Problem 7: The compounds [Co(SO4)(NH3)5]Br and [Co(SO4)(NH3)5Cl represent

(a) linkage isomerism (b) ionisation isomerism
(c) coordiantion isomerism (d) no isomerism

Solution: (d) Due to different molecular formula.

[ 182 ]
Coordination Compounds and Organometallics

Problem 8: What kind of isomerism exists between [Cr(H 2O)6 ]Cl3 (violet) and [Cr(H2 O)5Cl]H2 O
(greyish-green)?
(a) linkage isomerism (b) solvate isomerism
(c) ionisation isomerism (d) coordination isomerism

Solution: (b) Due to different position of under molecules.

Problem 9: IUPAC name of [Pt(NH3)2Cl(NO3)] is

(a) Platinum diamin3echloronitrite
(b) Chloronitrito N-ammineplatinum (II)
(c) Diamminechloridonitrito N-platinum (II)
(d) Diamminechloronitrito-N platinate (II)

Solution: (c) Self explanatory

Problem 10: Indicate the complex ion which shows geometrical isomerism
(a) Ma 2 b2 (b) Ma 4
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(c) Ma3 b (d) M(a – a)2

Solution: (a) Self explanatory

4.4 Bonding in Coordination Compounds

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Werner was the first to explain the bonding in coordination compounds. However, with the advancement
of theories of valence, modern theories have been proposed to explain some characteristic properties
of these compounds such as colour, geometry and magnetic properties. The main theories namely
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valence bond theory, crystal field theory and molecular orbital theory have been proposed. Various
theories are:
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Werner’s Coordination Theory

Werner isolated different complex compounds from the reaction of cobalt chloride and ammonia.
There are given below :
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Compound Colour

CoCl3.6NH3 Orange yellow

CoCl3 .5NH3 .H2 O Pink
CoCl3.5NH3 Violet
CoCl3.4NH3 Violet and green

Postulates of Werner's Coordination Theory

1. In coordination compounds, metal atoms exhibit two types of valencies namely, the primary
valency and the secondary valency.

The primary valency is ionizable whereas the secondary valency is non-ionizable. In modern
terminology, the primary valency corresponds to oxidation state and the secondary valency
corresponds to coordination number.

[ 183 ]
Coordination Compounds and Organometallics

2. Every metals atom has a fixed number of secondary valencies, i.e., it has a fixed coordination
number.

3. The metal atoms tend to satisfy both its primary as well as secondary valencies. Primary
valencies are satisfied by negative ions whereas secondary valencies are satisfied either by
negative ions or by neutral molecules or +ve ions. In certain cases, a negative ion may satisfy
both types of valencies.

4. The secondary valencies are always directed towards the fixed positions is space and this leads
to definite geometry of the coordination compound. For example, if a metal ion has six
secondary valencies, these are arranged octahedrally around the central metal ion. If the metal
ion has four secondary valencies, these are arranged in either tetrahedral or square planer
arrangement around the central metal ion. The secondary valencies, thus, determine the
stereochemistry of the complex. On the other hand, the primary valency is non-directional.

Thus, a metal atom exhibits primary valencies in the formation of its salts (e.g. CoCl3, AgNO3)
while the metal atoms exhibits its secondary valencies in the formation of its complex ions
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(e.g. [Co(NH3)6]3+, [Ag(NH3)2]+, etc.

Valence Bond Theory for Bonding in Coordination Compounds

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The main assumption of this theory are listed below :

1. The central metal ion in the complex makes available a number of empty orbitals for the
formation of coordinate bonds with suitable ligands. The number of empty orbitals made
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available for this purpose is equal to coordination number of the central metal ion. For example,
if coordination number is 6, six empty orbitals are made available and if coordination number
is 4, four empty orbitals are made available in the central metal ion.
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2. The appropriate atomic orbitals (s, p and d) of the metal hybridise to give a set of equivalent
orbitals of definite geometry such as square planar, tetrahedral, octahedral and so on.

Coordination number Hybridisation Geometry

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2 sp linear
3 sp 2 Trigonal planar
4 sp 3 Tetrahedral
4 dsp 2 Square planar
6 sp3 d2 or d2sp3 Octahedral

3. The d-orbitals involved in the hybridisation may be either inner d-orbitals i.e. (n–1) d or outer
d-orbitals i.e., nd. For example, in case of octahedral hybridisation, the orbitals may be two
of the 3d, one of 4s and three of 4p(d 2sp3) or one 4s, three 4p and two 3d(sp 3d 2
hybridisation).

4. Each ligand has at least one orbital (of donor atom) containing a lone pair of electrons.

5. The empty hybrid orbitals of metal ion overlap with the filled orbitals of the ligand to form
metal-ligand coordinate covalent bonds.

[ 184 ]
Coordination Compounds and Organometallics

Application to Complexes of C.N. 6.

(i) [Cr(NH3)6]3+ complex. The Chromium (Z=24) has the electronic configuration 3d54s1 as
shown below (a). The Chromium in this complex is in +3 oxidation state and the ion is formed
by the loss of one 4s and two of the 3d-electrons as shown below (b). The inner d-orbitals
are already vacant and two vacant 3d, one 4s and three 4p-orbitals are hybridised to form
six d2sp3-hybrid orbitals. Six pairs of electrons one from each NH3 molecule, (shown by xx)
occupy the six vacant hybrid orbitals. The molecule has octahedral geometry.

Since the complex contain three unpaired electrons, it is paramagnetic.

JE
ES

(ii) [Fe(CN)6]3– complex. Iron atom (Z=26) has the electronic configuration.3d64s2. In this
complex, Iron is in +3 oxidation state and has the electronic configuration 3d5 as shown below
It has been experimentally observed that the complex has one unpaired electron. To account
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for this, the two electrons in 3d-orbitals are paired up leaving two 3d-orbitals empty. These
six vacant orbitals (two 3d, one 4s and three 4p) hybridise to form d2sp3-hybrid orbitals. Six
pairs of electrons one from each CN– ion (shown by xx) occupy the six vacant hybrid orbitals.
ka

The molecule has octahedral geometry and is paramagnetic due to the presence of one
unpaired electron.
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(iii) [Fe(H2O) 6]3+ ion. In this case also, iron is in +3 oxidation state and has the electronic
configuration as 3d5. This complex has been found to be paramagnetic due to the presence
of five unpaired electrons. To account for this, the electrons in 3d-orbitals are not disturbed
and the outer 4d-orbitlas are used for hybridisation. The six orbitals (one 4s, three 4p and two
4d) are hybridised in resulting sp3d2-hybridisation. Six pairs of electrons, one from each water
molecule occupy the six hybrid orbitals. The molecule is octahedral and is paramagnetic.

[ 185 ]
Coordination Compounds and Organometallics

3d 4s 4p
(a) Fe-atom

(b) Fe (III)

(c) [Fe (H2O)6]3+

H2O H2O H2O H2 O H2 O H2O

(iv) [Fe(CN)6]4– ion. In this case, iron is in +2 oxidation state. The complex is diamagnetic and
therefore, it involves d2sp3-hybridisation as shown below :
JE
ES

Inner and Outer Orbital Complexes

From the above discussion it can be noted that in octahedral structures, the central metal may use
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inner (n–1)d orbitals or outer nd-orbitals for hybridisation. Therefore, the complexes may be
classified as :
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(a) Inner orbital complex. If the complex is formed by the use of inner d-orbitals for
hybridisation (written as d2sp3), it is called inner orbital complex. In the formation of inner
orbital complex, the electrons of the metal are forced to pair up and hence the complex will
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be either diamagnetic or will have lesser number of unpaired electrons. Such a complex is
also called as low spin complex.

(b) Outer orbital complex. If the complex is formed by the use of outer d-orbitals for
hybridisation (written as sp3d2), it is called an outer orbital complex. The outer orbital complex
will have larger number of unpaired electrons since the configuration of the metal ion remains
undisturbed. Such a complex is also called high spin complex.

Examples of Complexes of C.N. 4

In this case, the geometry will be tetrahedral or square planar depending upon whether
sp 3 or dsp 2 -hybridisation is involved.

(i) [Ni(CN)4]2– ion. The Nickel atom has the ground state electronic configuration as 3d84s2. In
this case Nickel is in +2 oxidation state and its electronic configuration is 3d8.

[ 186 ]
Coordination Compounds and Organometallics

Depending upon the type of hybridisation, there are two possible ways in which the complexes
of Nickel with coordination number 4 may be formed. If the complex involves dsp2 -
hybridisation, it would have square planar structure. For the formation of tetrahedral structure
the 3d-orbitals remain unaffected and, therefore, the two unpaired d-electrons remain as such.
Consequently, the complex would be paramagnetic like the Ni2+ ion itself.

On the other hand, for the formation of square planar structure through dsp2-hybridisation.
one of the 3d-orbitals should be empty and available for hybridisation. This is possible, if the
two unpaired d-electrons are paired up thereby making one of the 3d-orbitals empty. There
is thus no unpaired electron and the complex would be diamagnetic.

[Ni (CN)4]2– complex

We know from experiments that the complex [Ni(CN)4]2– is diamagnetic indicating that the
hybridisation involved in this case is dsp2, as represented. The dotted arrows represents,
electrons pairs donated by CN– ions. The ion has a square planar geometry.
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3d 4s 4p
(a) Ni Atom

(b) Ni (II)
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2–
(c) [Ni (CN)4]

CN– CN– CN– CN–

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(ii) [NiCl4)]2– ion. The nickel (II) ion has two unpaired electrons as shown below in (a). The
magnetic measurements of the complex [NiCl4]2– show that it is paramagnetic and has two
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unpaired electrons. Therefore, in this case the 3d-orbitals remain undisturbed and sp 3-
hybridisation occurs resulting in tetrahedral structure of the complex. As is evident from Fig.
(b) there are two unpaired electrons in the complex.
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3d 4s 4p
(a) Ni-atom

(b) Ni-(II)

(c) [NI Cl4]2–

Cl– Cl– Cl– Cl–

(iii) [Ni(CO)4]. The Nickel(0) has 3d84s2 as its outer electronic configuration. For complexes with
coordination number 4, the central atom may be involved is sp3 or dsp2 type of hybridisation,
for each of which the 4s-orbital must be empty. The electrons of 4s orbitals are forced into
the 3d-orbitals to pair up with the two unpaired d-electrons. Therefore, the complex is
diamagnetic. This results in sp3 hybridisation and the complex has tetrahedral structure.

[ 187 ]
Coordination Compounds and Organometallics

(iv) Exceptional [Cu(NH3)4]2+ SO42–

Limitations of Valence Bond Theory

(i) It give only the qualitative explanations for complexes.

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(ii) It does not explain the detailed magnetic properties of the complexes.

(iii) This theory does not explain the absorption spectra of complexes.

(iv) It does not explain the relative stability of different complexes.

ES

These properties are more satisfactorily explained by the ligan field theory. This theory takes into
account the splitting up of the degeneracy of the five d-orbitals in the field of ligands. The extent
of splitting depends upon the metal d-orbitals, nature and number of ligands.
an

Crystal Field Theory

The Crystal Field Theory (CFT) was originally proposed for explaining the optical properties of
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crystalline solids. It was applied to the study of coordination compounds in the 1950s.

The valence bond theory considers the bonding between the metal ion and the ligands as purely
covalent. On the other hand, crystal field theory is based on the assumption that the metal ion and
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the ligands act as point charges and the interactions between them are purely electrostatic.
In case of negative ligands (anions such as Cl–, Br–, CN–), the interactions with metal ions are ion-
ion interactions. If the ligands are neutral molecules (such as NH3, H2O, CO), the interactions with
the metal ions are ion-dipole interactions. For example, in the case of complex ion [CoF6]3– the
interactions are between Co3+ and F– ions whereas in [Co(NH3)6]3+, the interactions are between
negatively charged and of NH3 molecules (-charge on N atom) and Co3+ ion.

In the case of free metal ion, all the five d-orbitals have the same energy. These orbitals having the
same energies are called degenerate orbitals.This means that an electron can occupy any one of
these five d-orbitals with equal energy. However, on the approach of the ligands, the orbital electrons
will be repelled by the line pairs (or negative charges) of the ligands. The repulsion will raise the
energy of the d-orbitals. If all the ligands approaching the central metal ion are at equal distance
from each of the d-orbitals, the energy of each orbital will increase by the same amount, due to
spherical field or symmetrical field of ligands. Therefore, these orbitals will still remain degenerate,

[ 188 ]
Coordination Compounds and Organometallics

but they will have higher energy than that of the free ion. But we know that d-orbitals have different
orientations and, therefore, these orbitals will experience different interactions from the ligands. The
orbitals lying in the direction of the ligands,will experience greater repulsion and their energies will be
raised relative to their positions in a symmertrical field. (Remember that orbitals represent regions of
negative charge; because like charges repel each other and therefore, potential energy increases
when they are brough together). On the other hand, the orbitalysing away from the approach of the
ligands will have lesser interactions with the negative charge of donor atoms and therefore, their
energies will be lower than they would be in a spherical field. Therefore, due to the electrical field of
the ligands, the energies of the five d-orbitals will split up. This conversion of five degenerate
d-orbitals of the metal ion into different sets of orbitals having different energies in the presence
of electric field of ligands is called crystal field spliting. This concept forms the basis of Crystal
Field Theory.

This splitting of d-orbitals is shown in figure.

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d x2 - y2 d z2 (e g )
ES

Average energy of
d-orbitals in a spherical
crystal field
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d-orbitals in free metal ion dxydyzdzx(t2g)

splitting of d-orbitals

Thus, in coordination compounds, the interaction between the ligand and the metal ion causes the
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five d-orbitals to split up. The number of ligands (coordination number) and their arrangement
(geometry) around the central metal ion will have different effect on the relative energies of the five
d-orbitals. In other words, the crystal field splitting will be different in different structures with
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different coordination numbers.

For example, in case of octahedral complexes, the five d-orbitals split up into two sets; one set
consisting of two orbitals d x 2  y2 and d z2 of higher energy and another set consisting of three orbitals
(dxy, dyz and dzx) of lower energy.

The energy difference between the two sets of energy levels is called crystal field splitting energy
and is represented as 0 (the subscript ‘o’ stands for octahedral). It measures the crystal field
strength of the ligands.

It may be noted that the crystal field splitting occurs in such a way that the average energy of the
d-orbitals does not change. This is known as barycentre rule, which is similar to ‘centre of gravity’
type rule. This means that the three orbitals lie at an energy that is 2/5 0 below the average d-orbital
energy and the two d-orbitals lie at an energy 3/5 0 above the average energy.

[ 189 ]
Coordination Compounds and Organometallics

Spectrochemical Series

The crystal field splitting (0) depends upon the nature of the ligands. The graeter the ease with
which the ligand can approach the metal ion, the greater will be the crystal field splitting caused by it.
The ligands which cause only a small degree of crystal field splitting are called weak field ligands
while those which cause a large splitting are called strong field ligands.

Thus, the ligands can be arranged according to the magnitude of the 0 and this arrangement is
called spectrochemical series. The spectrochemical series in the increasing order of crystal field
splitting is given below :

Weak field ligands

I– < Br– < SCN– < Cl– < S2– <NO3– < F– < OH– < OX2– < O2– < H2O < NCS– < edta4– < NH3 < en
< dipy < o-phen < NO2– < CN– < CO

Increasing crystal field : The above spectrochemical series is an experimentally determined series
based on the absorption of light by complexes with different ligands. From the series it is clear that
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CO, CN– and NO2– are strong field ligands whereas I–, Br– and Cl– are weak field ligands. In
general, the ligands lying above H2O are called strong field ligands and they cause greater crystal
field splitting (or high 0). On the other hand the ligands lying below water are called weak field
ES

ligands and they cause lesser crystal field splitting (or low 0).

Similarly, it can be shown from the geometry, that in tetrahedral complexes, the two d-orbitals ( d x 2  y 2
and d x 2 called ‘e’) become more table and of lower energy and the three orbitals ( d xy , d yz and d zx
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called t2) become less stable and of higher energy as shown below :

(t2)g
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dxy dxz dzx
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d x 2 - y2 d z 2 (e)g

Tetrahedral Field Splitting of d-orbitals

The energy difference between these two sets is called crystal field splitting in tetrahedral field and
is abbreviated as t (the subscript ‘t’ indicates tetrahedral complexes). It has been observed that the
splitting in tetrahedral complexes (t) is considerably less than in octahedral complexes (0). It has
been found that t  4 / 5  0 . It may be noted that the splitting of d-orbitals in square planar complexes
is complicated.

Electronic Structures and Properties of complexes according to C.F. theory : The electronic
configurations of complexes depend upon the crystal field splitting. We have learnt that in octahedral
complexes, the three orbitals are of lower energy and two orbitals are of higher energy. According to

[ 190 ]
Coordination Compounds and Organometallics

Hund’s rule, electrons occupy a set of orbitals of same energy one at a time with their spins parallel.
The electrons only pair up after each orbital gets one electron. So, for complexes having upto three
d-electrons (d1, d2 and d3) each electron can occupy a separate orbital in the lower set as shown
below :

1 2 3
d complex d complex d complex
1 2 3
t2g t2g t2g

For a d4 complex, there are two possibilities :

(i) All the four electrons may occupy lower set of orbitals with one electron gets paired, i.e., t2g4. It
experiences a strong repulsion from the electron already there.
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(ii) The three electrons occupy lower set of orbitals and the fourth electron goes to one of the higher
set of orbitals i.e., t2g3 eg1.

Which electronic configuration is possible or has the lower energy depends upon the relative magnitude
ES

of the crystal field splitting (0) and the pairing energy, P (P represents the energy required for
electron pairing in a single orbital). The crystal field splitting energy depends upon the nature of
ligands attached. If 0 is large (as it is for strong field ligands), the electrons will try to remain in the
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lower set of orbitals. In this case, the complex has less number of unpaired electrons and is called
low spin complex.
In this case the repulsion due to pairing of electrons will be less than 0.
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On the other hand, if 0 is small (as it is for weak field ligands), then after filling the lower set of three
orbitals with one electron each, the next electron goes to the higher set of orbitals. In this case, the
repulsion due to pairing of electrons will be more than 0. The pairing of electrons will occur only
after all the five orbitals are singly filled. In this case, the complex will have maximum number of
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unpaired electrons and is called high spin complex.

Thus, the actual configuration adopted by the complex is decided by the relative values of 0 and P
where P represents the energy required for electron pairing in a single orbital.
 If 0 is less than P(0 < P), we have weak field, the fourth electron will enter one of the e.g.,
orbitals giving the configuration, t2g3eg1. It will be high spin complex.
 If 0 is more than P(0 > P), we have strong field and the pairing will occur in the t2g orbitals with
eg orbitals remaining unoccupied giving the configuration t2g4. It will be low spin complex.
Thus, we can easily predict whether an octahedral complex is likely to be high spin or low spin
complex by noting the position of the ligands in the spectrochemical series. In general,
Strong field ligands form  Low spin complexes
Weak field ligands form  High spin complexes
Magnetic behaviour of complexes: The magnetic properties of coordination complexes can be
easily explained on the basis of crystal field spliting theory.

[ 191 ]
Coordination Compounds and Organometallics

Let us consider the complexes of Fe (III) such as [Fe(CN)6 ]3– and [Fe(H2O)6]3+. Fe3+ has 3d5
electronic configuration having five electrons. Now, CN– is a strong field ligand and we expect large
splitting of d-orbitals. As a result, the five d-electrons will true to remain in lower set and will pair up,
i.e., t2g5. This results in low spin complex which will have only one unpaired electron. On the other
hand, H2O is a weak field ligand and we expect small splitting of d-orbitals. As a result, after filling
one electron each in lower set of orbitals, the remaining two electrons will go the the higher set of
orbital, i.e., t2g3eg2. Thus, the complex will be paramagnetic due to the presence of five unpaired
electrons. It is also called high spin complex.

Let us consider the examples of [CoF6]3– and [Co(NH3)6]3+ complexes,

JE
ES

t2g6eg°
an
ka

Cobalt in [Co(NH3)6]3+ and [CoF6]3+ is in +3 oxidation state and it has six d-electrons. It has been
observed that F ion is a weak field ligand and therefore, 0 is small. The complex will be high spin
having the configuration t2g4 eg2. As clear from the figure, the complex is paramagnetic due to the
lp

presence of four unpaired electrons. On the other hand, NH3 is a strong field ligand and therefore,
the electrons pair up having the configuration t2g6 eg0. This results in low spin [Co(NH3)6]3+ complex.

Factors determining the magnitude of the orbital splitting energy 

The following factors influence the magnitude of :

Nature of ligand. The  value depends upon the nature of the ligand. The greater the ease with
which the ligands can approach the metal ion and interact with it, the greater will be the crystal field
splitting energy. The ligands which cause only small  value are called weak field ligands while
those which cause a large  value are called strong field ligands.

The ligands can be arranged in the increasing field strength in spectrochemical series.

Oxidation state of the metal ion. In general, the higher the ionic charge on the central metal ion,
the greater the value of . Therefore, the metal ion with higher oxidation state causes larger  than

[ 192 ]
Coordination Compounds and Organometallics

is done by the ion with lower oxidation state. For example,  for the entity [Co(H2O)6]3+ will be more
than  for the entity [Co(H2O)6]2+ because oxidation state of cobalt is +3 in the first and +2 in the
second.

Nature of the metal ion. For the analogous entities within a group,  values differ. The  value for
similar complexes in the same oxidation state increases by (30-50%) on going from 3d series (first
transition series) to 4d series (second transition series) to 5d series (third transition series). As a
consequence of this, coordination entities of second and third transition series have a greater tendency
to form low spin complexes as compared to the first transition series.

Geometry of the coordination entity. The  value for tetrahedral coordination entities is about
half the  value for octahedral entities, i.e.

4
t  0
9
Illustration 1: Why are low spin tetrahedral complexes not formed?
JE

Solution: This is because for tetrahedral complexes, CFSE is lower than pairing energy.

Illustration 2: Give the electronic configuration of the following complexes on the basis of Crystal Field
ES

Splitting theory.

[CoF6 ]3–, [Fe(CN)6]4– and [Cu(NH3)6]2+

an
4 2
Solution: [CoF6]3– has Co3+ (d6) vss. t 2g eg

6 0
[Fe(CN)6]4– has Fe2+ (d6) viz. t 2g eg
ka

6 3
[Cu(NH3)4]2+ and Cu2+ (d9) viz. t 2g eg

Illustration 3: Explain why [Fe(H2O)6]3+ has magnetic moment value of 5.92 B.M. whereas [Fe(CN)6]3+
lp

has a value of only 1.74 B.M.

Solution: H2O is weak ligand so electron do not pair up. While CN is strong ligand so electron pair up.

Illustration 4: Arrange following complex ions in increasing order of crystal field splitting energy (0).

[Cr(Cl)6]3–, [Cr(CN)6]3– , [Cr(NH3)6]3+

Solution: From spectrochemical series, CFSE of ligands is in the order: Cl– < NH3 < CN–

Illustration 5: Why do compounds having similar geometry have different magnetic moment?

Solution: The difference is due to presence of weak and strong ligands. If ligand is strong (high
CFSE), electron in d-subshell will pair up and magnetic moment will be low. If ligand is weak
(low CFSE), electron will not pair up. Hence, magnetic moment will be high, e.g. [CoF6]3–
and [Co(NH3)6] both are octahedral but former is paramagnetic while latter is diamagnetic.

[ 193 ]
Coordination Compounds and Organometallics

SAMPLE PROBLEMS 4.4 (MCQ)

Problem 1: The complex ion [Cu(NH3)4]2+ is
(a) Tetrahedral and paramagnetic (b) Tetrahedral and diamagnetic
(c) Square planar and paramagnetic (d) Square planar and diamagnetic

Solution: (c) dsp2 hybridisation and presence of unpaired electron.

Problem 2: The hybridization involved in [Ni(CO)4] is

(a) sp 3 (b) dsp 2
(c) sp 3 d (d) d 2 sp 3

Solution: (a) Self explanatory

Problem 3: Which of the following is an outer orbital complex ?

(a) [Fe (CN)6 ]3– (b) [Fe (CN)6 ]4–
(b) [Fe F6]3– (d) [Cr (CN)6]3–
JE

Solution: (c) sp3d2 hybridisation

Problem 4: The complex [Co(NH3)6]Cl3 in aqueous solution ionizes to give a total number of ions
equal to
ES

(a) 0 (b) 2
(c) 3 (d) 4

Solution: (d) [Co(NH3)6]3+ + 3Cl–

an

Problem 5: Which one of the following statements is incorrect ?

(a) Greater the stability constant of a complex ion, greater is its stability.
(b) Greater the charge on the central metal ion, greater is the stability of the complex.
ka

(c) Greater is the basic character of the ligand, the greater is the stability of the complex.
(d) Chelate complexes have low stability constants.
lp

Solution: (b) Greater the charge on the central ion, greater is the stability of the complex.

Problem 6: The stability constants of the complexes formed by a metal ion (M2+) with NH3, CN–, H2O
and en are of the order 1011, 1027, 1015 and 108 respectively. Then
(a) en is strongest ligand
(b) CN– is the strongest ligand
(c) These values cannot predict the strength of the ligand
(d) All ligands are equally strong

Solution: (b) Higher the stability constant stronger is ligand.

Problem 7: Crystal field stabilization energy for high spin d4 octahedral complex is
(a) –0.6 0 (b) –1.8 0
(c) –1.6 0 + P (d) –1.2 0

Solution: (a) t2g3eg1= 3 (–0.4) + (0.6) = –0.60

[ 194 ]
Coordination Compounds and Organometallics

Problem 8: The spin magnetic moment of cobalt in the compound HgCo(SCN)4] is

(a) 3 (b) 8

(c) 15 (d) 24

Solution: (c) Calculate number of unpaired electron and apply n ( n  2) .

Problem 9: Which of the following shall form an octahedral complex?
(a) d4 (low spin) (b) d8 (high spin)
(c) d6 (low spin) (d) all of these

Solution: (c) is d6 low spin two d-orbital are vacant.

Problem 10: [Cr(H2O)6 ]Cl3 (at. mno. of Cr = 24) has a magntic moment of 3.83 B.M. The correct
distribution of 3d electrons in the chromium of the complex is
1 1 1 1 1 1
(a) 3d xy , 3d yz , 3d xz (b) 3d xy , 3d yz , 3d x 2
JE

1 1 1 1 1 1
(c) 3d (x 2 y2 ) , 3d z2 , 3d xz (d) 3d xy , 3d( x 2 y2 ) , 3d yz

Solution: (a) Calculate number of unpaired electron.

ES

4.5 Colour in Coordination Compounds

One of the achievements of crystals field theory is its ability to explain the colours of transition metal
an

complexes. As we have learnt in the previous unit, most of the transition metal complexes are
coloured in their solid or solution form. The transition metals have the property to absorb certain
radiations from the visible region of the spectrum and as a result, the transmitted or reflected light is
ka

coloured. The visible light (white light), as we know is a mixture of radiations of many wavelengths
ranging from blue (about 400 nm) to red (about 700 nm). When some of these wavelengths are
removed from a beam of white light by passing the light through a sample, then the transmitted light
lp

is no longer white. For example, if red light (long wavelength) is absorbed from white light, then it
appears to us to be green (short wavelength). On the other hand, if green light (short wavelength) is
absorbed then it appears to us to be red. Red and green colours are called complementary colours.
Thus, the colour we see of a complex in a solid or in a solution is due to the light which is not
absorbed but which is transmitted (complementary colour).

In the case of transition metal complexes, the energy difference between two sets of d-orbitals is
very small. When visible light falls on them, the electron raised from lower set of orbitals to higher set
of orbitals. For example, in case of octahedral complexes, the electron goes from set of dxy, dyz, dzx to
set of d x 2  y 2 orbitals. As a result of absorption of some selected wavelength of visible light corresponding
to energy difference between these sets of energy levels, the transmitted light gives colour to
complexes. For example, the complex [Ti(H2O)6]3+ is purple.

In this complex, the metal ion has d1 configuration. In ground state this electron occupies one of the
lower set of orbitals having the electronic configuration, t2g 1. The next higher energy state eg is

[ 195 ]
Coordination Compounds and Organometallics

available for the excitation of electron. When white light passes through the complex, the electron
gets excited from the lower set of orbitals (t2g) to one of the higher set of orbitals, eg ( d x 2  y 2 or
d z 2 orbital) by absorbing light equal to 0.

This may be expressed as

t 12 g eg0 
 t 20g e1g

This is shown below:

hv

light

absorbed

t21 g eg0 t20g e1g

Ground State Excited State
JE

Transition of one electron from lower orbital to higher

orbital in [Ti(H2O)6]3+ complex.
ES

The energy corresponding to this transition corresponds to green and yellow lights which are absorbed
from the white light, while the blue and red portions are emitted. The solution of complex [Ti(H2O)6]3+,
therefore, looks purple.
an

Since, the difference between different sets of orbitals in octahedral complexes vary from on metal
ion to another and the nature of the ligands, therefore, different complexes absorb different amounts
of energies from visible region and exhibit different colours. For example, let us consider three
ka

complexes of Co3+ as [Co(H2O)6]3+, [Co(NH3)6]3+ and [Co(CN)6]3–. According to spectrochemical

series, the crystal field splitting energies will be in the order of ligands as:

H2O < NH3 < CN–

lp

Therefore, excitation energy will be smallest (largest wavelength absorbed) for [Co(H2O)6]3+ complex
and largest Z (smallest wavelength absorbed) for [Co(CN)6]3– complex. That is why, [Co(H2O)6]3+
absorbs orange colour and appears blue and [Co(CN)6]3– absorbs violet colour and appears as
yellow.

[Co(H2 O)6 ] 3+ [Co(NH 3 )6 ] 3+ [Co(CN)6 ] 3–

0 value Small Intermediate Large

Excitation energy (E) Small Intermediate Large
Absorption wavelength () Large Intermediate Small
Colour absorbed Orange Blue Violet
Colour transmitted Blue Yellow orange Yellow

The relationship between the wavelength of light absorbed and the colour observed in some coordination
entities as given in Table.
[ 196 ]
Coordination Compounds and Organometallics

Relationship between the wavelength of light absorbed and the colour

observed in some coordination entities

Coordination entity Wavelength Colour of light Colour coordination

of light absorbed (nm) absorbed entity (transmitted)

[Co(CN)6 ]3– 310 Violet Pale Yellow

[Co(NH3 )6 ]3+ 475 Blue Yellow orange
[Co(H2 O)(NH3 )5 ]3+ 500 Blue green Red
[Ti(H2O)6 ]3+ 510 Blue green Purple
2+
[CoCl(NH3)5] 535 Yellow Violet
3+
[Cu(H2O)6 ] 600 Red Blue

It may be noted that in the absence of ligands, the crystal field splitting does not occur and hence the
substance is colourless. For example, removal of water from [Ti(H2O)6]Cl3 on heating makes it
colourless. Similarly, anhydrous CuSO4 is white, but CuSO4.5H2O is blue in colour.
JE

The effect of the ligand on the colour of a complex may be illustrated by taking the example of
[Ni(H2O)6]2+. This is formed when Nickel chloride is dissolved in water. The aqueous solution of the
complex has green colour. If the didentate ligand, Ethane-1,2-diamine (en) is progressively added in
ES

the molar ratio of en : Ni as 1 : 1, 2 : 1 and 3 : 1, the following series of reactions occur resulting
different colour changes as:

[Ni(H 2 O) 6 ]2  (aq)  en(aq) 

[Ni(H 2 O)4 en]2   H 2 O
an
Pale blue

[Ni(H 2 O)4 en]2  (aq)  en(aq) 

 [Ni(H 2 O) 2 (en)]2 (aq)  2H 2O
Blue / purple
ka

[Ni(H 2 O) 2 (en) 2 ]2  (aq)  en(aq) 

 [Ni(en)3 ]2 (aq)  2H 2O
Violet

These colour changes are observed due to the presence of different ligands in the complexes.
lp

It may be noted that only those transition metal complexes are coloured which have incomplete
d-subshells. The transition metal ions have completely filled or completely empty d-subshells are
colourless. For example, complexes of Cu+ (d10), Zn2+ (d10), Ag+ (d10), Ti4+ (d0), etc. are colourless.

Colour of Some Gemstones

The colours of many familiar gemstones are due to the presence of transition metal ions. In these,
the colours are produced due to electronic transitions within d-orbitals (called d-d transitions) of a
transition metal ion. For example, the mineral Corundum Al2O3 (aluminium oxide) is colourless when
pure. However, when various M3+ transition metal ions are present in trace amounts various gemstones
are formed. Ruby is Aluminium oxide containing about 0.15 – 1% Cr3+ ions which are randomly
distributed in positions normally occupied by Al3+. We may imagine these Chromium (III) species as
octahedral Chromium (III) complexes incorporated into alumina lattice. The d-d transitions at these
centres give rise to brilliant red colour.

[ 197 ]
Coordination Compounds and Organometallics

Transition metal Name Colour

Cr3+ (in corundum) Ruby Brilliant red

3+
Fe (in corundum) Topaz (yellow sapphire) Yellow to reddish yellow
Mn3+ (in corundum) Amethyst Deep purple
Co3+ or V3+ (in corundum) Blue sapphire Ruby blue
3+
Cr (in beryl) Emerald Green
3+
Fe (in beryl) Aquamarine Pale blue to light greenish blue

Stability of Coordination Compounds in Solution

Most of the complexes are highly stable. The interaction between metal ion and ligand
may be regarded as Lewis acid-base reaction. If the interaction is strong, the complex
formed would be thermodynamically more stable. Let us consider the equilibrium reaction
between metal ion (M a+ ) and n ligands (L x– ) to form the complex [ML n] b+
JE

Ma+ + n Lx– [MLn]b+

where a+, x– and b+ are the charges on the metal, ligand and complex respectively. Charge balance
requires that
ES

(a+) + n(x–) = (b+)

The stability constant for the above general reaction may be written as
an
b
[ML n ]
K=
[M a  ] [Lx  ] n

The value of the magnitude of K gives as indication of the stability of the complex in solution. The
ka

values of K for a few reaction re given below :

System K
lp

Ag + + 2NH 3 [Ag(NH3 )2 ]+ 1.6 × 10 7

Ag + + 2CN – [Ag(CN) 2 ]– 5.4 × 10 18

Cu 2+ + 4NH 3 [Cu(NH 3)4 ]2+ 4.5 × 10 21

Cu 2+ + 4CN – [Cu(CN) 4 ] 2– 2.0 × 10 27

Co 3+ + 6NH 3 [Co(NH 3 )6 ]3+ 5.0 × 10 33

The above values give very interesting observations. The values indicate that CN– ion is a stronger
ligand than NH3 molecule because the stability constants for cyanide complexes are very large in
comparison to corresponding ammine complexes.

Ni2+ + 6NH 3 [Ni(NH 3 ) 6 ] 2+ ; K = 6 x 10 8

Ni2+ + 3en [Ni(en) 3 ] 2+ ; K = 4 x 10 18

[ 198 ]
Coordination Compounds and Organometallics

The K values indicate that the bidentate ligand NH2CH2CH2NH2 forms a considerably more stable
complex than ammonia.

Factors affecting the stability of a complex ion. The stability of a complex ion depends
upon the following factors :

1. The nature of the central metal ion. In general, the greater the charge density on the
central ion, the greater is the stability of its complexes. In other words, the greater the charge
and the smaller the size of an ion, i.e., (the larger the charge/radius ratio of an ion), the greater
is the stability of its complexes. For instance, Fe3+ ion carries higher charge than Fe2+ ion but
their size is about the same. Hence, charge density is higher on Fe3+ than on Fe2+ ion. The
complexes of Fe3+ ion are, therefore, more stable.

Fe 3+ + 6CN – [Fe(CN) 6 ] 3– ; K = 1.2 x 10 31

Fe 2+ + 6CN – [Fe(CN) 6 ] 4– ; K = 1.8 x 10 6

JE

The order of stability of complexes of some of the ion carrying the same charge but differing
in ionic radii also support the above view. In general,

Ion Cu 2+ > Ni2+ > Co2+ > Fe 2+ > Mn2+

ES

Ionic radius (pm) 69 78 82 83 91

All these ions carry the same charge but the size increases as one moves from Cu2+ to Mn2+.
Hence, complexes of Cu2+ are most stable while those of Mn2+ are least stable.
an

2. The nature of the ligand. The more basic a ligand, the greater is the ease with which it
can donate its lone pairs of electrons and, therefore, the greater is the stability of the complexes
formed by it. Thus, CN– and F– ions and NH3 molecules, which are strong bases, are also
ka

good ligands and form many stable complexes.

For anionic ligands, the higher the charge and the smaller the size, the more stable is the complex
formed. Thus, F– ion gives more stable complexes than does Cl– ion.
lp

General Method of Preparation of Coordination Compounds

Coordination compounds are generally prepared by common methods such as substitution reactions,
redox reactions and by the direct combination of the reactants. These are briefly discussed below :

1. Substitution reactions. The majority of complexes are prepared by substitution reactions.

The general method of synthesis is to replace water molecules surrounding the metal ion by
other ligands. For example, when an aqueous solution of CuSO4 is heated with excess of
ammonia, it gives deep blue coloured [Cu(NH3)4]2+ species.

[Cu(H2O)4]2+ + 4NH3 [Cu(NH3)4]2+ + 4H2O

deep blue

Cobalt (II) nitrate reacts with concentrated aqueous ammonia and NH4NO3 in the presence
of H2O2 to give the complex, Pentaamminenitrocobalt (III) nitrate as

[ 199 ]
Coordination Compounds and Organometallics

2[Co(H2O)6](NO3)2 + 8NH3 + 2NH4NO3 + H2O2 2[Co(NO2)(NH3)5] (NO3)3

+ 14H2O

Some other examples are :

[Co(NO2)6]3– + 2 en [Co(en)2(NO2)2]+ + 4NO2

[Ni(H2O)6]2+ + 6NH3 [Ni(NH3)6]2+ + 6H2O

2. Redox reactions. Hexaamminecobalt (III) chloride can be prepared by the oxidation of an

aqueous solution of Cobalt (II) chloride made alkaline with ammonia in the presence of NH4Cl
and hydrogen peroxide.

2CoCl2 + 2NH4Cl + 10NH3 + H2O2 2[Co(NH3)6]Cl3 + 2H2O

(aq.)

An aqueous solution of oxalic acid and potassium oxalate reduces K2Cr2O7 to the complex
ion trioxalatochromate (III) ion.
JE

K2Cr2O7 + 7H2C2O4 + 2K2C2O4 2K3 [Cr(C2O4)3] + 6CO2 + 7H2O

3. Direct combination of reactants. Metal ammines can be prepared by the direct addition of
ES
a metal salt to liquid ammonia.

NiCl2 + 6NH3 [Ni(NH3)6] Cl2

CoCl3 + 6NH3 [Co(NH3)6] Cl3

an

AgCl + 2NH3 [Ag(NH3)2] Cl

Similarly, addition of Ethylendiamine (en) to PtCl2 gives [Pt(en)2]Cl2.

ka

PtCl2 + 2 en [Pt (en)2] Cl2

Applications of Coordination Compounds

lp

1. Estimation of hardness of water. Hardness of water is estimated by simple titration with

EDTA. The Ca2+ and Mg2+ ion form stable complexes with EDTA.

2. In qualitative analysis. The complex formation method is used in qualitative scheme of group
I for the separation of Silver ion from the precipitate of AgCl, Hg2Cl2 and PbCl2.

AgCl + 2NH3 [Ag(NH3)2] Cl

Soluble

Hg2Cl2 and PbCl2 do not form complexes and therefore, do not dissolve.

3. In electroplating. The coordination compounds of Silver and Gold are used as constituents
of electroplating baths for controlled delivery of metal ions for reduction.

4. In water treatment. complex compound like sodium metapolyphosphate are used to remove
Ca2+ and Mg2+ ions from hard water by forming complexes with these ions.

[ 200 ]
Coordination Compounds and Organometallics

5. In dyeing. Mordants are insoluble substances which are uniformly deposited in the fibers to
be dyed. These mordants can then attach to the molecules of the dyes by complex formation
and help in fixing the dye to the fibres in a stable form. The important mordants used are
Fe(OH)3 and Al(OH)3.

6. Biological importance. Many biological important natural compounds exist as coordinated

complexes. For example,

Chlorophyll : a complex of Mg 2+ ,
Haemoglobin : a complex of Fe2+ ,
Vitamin B 12 : a complex of Co 3+

7. In metallurgical processes. Complex formation techniques are also used for the extraction
of metal such as Gold and silver.
JE

Ag2S + 4NaCN 2Na[Ag(CN)2] + Na2S

2Na[Ag(CN)2] + Zn Na2[Zn(CN)4] + 2Ag

Silver
ES

8. In medicines. Complexing agents are used for removal of metal poisoning. Recently, a
platinum complex cis [PtCl2(NH3)2] known as cisplatin has found use in cancer chemotherapy.
an

9. In catalysis. Certain coordination compounds act as catalysis for different reactions. For
example, Pentacarbonylcobalt(II) acts as a catalyst in the hydrogenation of alkenes. During
hydrogenation, Co(II) is oxidised to Co(III).
ka

Illustration 1: Calculate the overall complex dissociation equilibrium constant for the Cu(NH 3 ) 42 ion,
given that 4 for this complex is 2.1 × 1013.
lp

Solution: Overall stability constant (4) = 2.1 × 1013

Overall dissociation constant is the reciprocal of the overall stability constant. Hence,
1 1 14
overall dissociation constant = β  2.1 1013  4.7 10 .
4

Illustration 2: Aqueous copper sulphate solution (blue in colour) gives (i) a green precipitate with
aqueous potassium fluoride, and (ii) a bright given solution with aqueous potassium chloride.
Explain these experiment results.

Solution: Aqueous CuSO 4 solution exists as [Cu(H 2O) 4]SO 4 which has blue colour due to
[Cu(H2O)4]2+ ions.

(i) When KF is added the weak H2O ligands are replaced by F– ligands forming [CuF4]2–
ions which is a green precipitate.

[Cu(H 2O) 4 ]2  4F  

 [CuF4 ]2  4H 2O
Tetrafluorocuprate (II)
(Green ppt.)

[ 201 ]
Coordination Compounds and Organometallics

(ii) When KCl is added, Cl– ligands replace the weak H2O ligands forming [CuCl4]2– ion
which has bright green colour.

[Cu(H 2O) 4 ]2  4Cl 

 [CuCl4 ]2  4H 2O
Tetrachloroocuprate (II)
(Green solution)

Alternatively, we can write the reaction as:

CuSO4 (aq)  4KF(aq) 

 K 2 [CuF4 ]  K 2SO 4

CuSO4 (aq)  4KCl(aq) 

 K 2 [CuCl4 ]  K 2SO4

Illustration 3: CuSO45H2O is blue in colur while CuSO4 is colourless. Why?

Solution: In CuSO4.5H2O, 4H2O molecules are present as ligand. Crystal field splitting occurs and
hence 4d transition occurs which give it blue colour. In CuSO 4 there are no H 2O
molecules present as ligand. No crystal field splitting occurs and hence it has no colour.
JE

Illustration 4: Arrange the following complexes in the increasing order of conductivity of their solution:

[Cu(NH3)3Cl3], [Cu(NH3)4Cl]Cl, [Cu(NH3)4]Cl2, [Cr(NH3)3Cl]Cl3

ES

Solution: [Cr(NH3)3Cl3] < [Cu(NH3)4Cl]Cl < [Cu(NH3)4]Cl2 < [Cu(NH3)3Cl]Cl3

This is the order because ion produced are 0, 2, 3 and 4 respectively.

SAMPLE PROBLEMS 4.5 (MCQ)

an

Problem 1: The oxidation state of Fe in the brown ring complex [Fe(H2O)5NO]SO4 is

(a) +1 (b) +2
ka

(c) +3 (d) +4

Solution: (a) [x + (0 × 5) + 1] = 2 or x = + 1
lp

Problem 2: For the given complex [CuCl2 (en) (NH3)2]+, the number of geometrical isomers, the number
of optical isomers and total number of isomers of all type possible respectively are
(a) 2, 2 and 4 (b) 2, 2, and 3
(c) 2, 0 and 2 (d) 0, 2 and 2

Solution: (c) Due to symmetrical structure there is no optical isomerism.

Problem 3: Excess of silver nitrate solution is added to 100 ml of 0.01 M pentaaquachloromium (III)
chloride solution. The mass of silver chloride obtained in grams is (Atomic mass
of silver is 108)
(a) 287 × 10–3 (b) 143.5 × 10–5
(c) 143.5 × 10–2 (d) 287 × 10–2

Solution: (a) 2Ag  2Cl 

 2AgCl

[ 202 ]
Coordination Compounds and Organometallics

Problem 4: Both Cu3+ and Pt4+ have a coordination number of six. Which of the following pair of
complexes will show approximately the same electrical conductance for their 0.001 M aqueous
solutions?
(a) CuCl3, 4NH3 and PtCl4, 4 NH3 (b) CuCl3, 3NH3 and PbCl4, 5 NH3
(c) CuCl3, 6NH3 and PtCl4, 5 NH3 (d) CuCl3, 6NH3 and PtCl4, 6 NH3

Solution: (c) Self explanatory

Problem 5: Which of the following complex ions is expected to absorb visible light?
(a) [Ti(en)2(NH3)2]3+ (b) [Cr(NH3)6]3+
(c) [Zn(NH3)6]2+ (d) [Sc(H2O)3(NH3)3]3+
[At. No. zn = 30, Sc = 21, Ti = 22, Cr = 24]

Solution: (b) Due to presence of unpaired electron.

Problem 6: The ratio of the uncomplexed to the complexed Zn2+ ion in a solution of 10 M NH3 is (Given
that the stability constant of [Zn(NH3)4]2+ is
(a) 3.3 × 10–9 (b) 3.3 × 10–11
(c) 3.3 × 10–13 (d) 3.3 × 10–14
JE

Solution: (d) Self explanatory

Problem 7: Which of the following reactions are kinetically favourable?

ES

I. [Cu(H 2O) 4 ]2  4NH 3 

[Cu(NH3 )4 ]2  4H 2O

II. [Cu(H 2O) 4 ]2  4Cl 

[CuCl4 ]2  4H 2O

III. [Co(H 2 O)6 ]3  6Cl 

[Co(Cl6 )3  6H 2O
an

(a) I and II (b) II and III

(c) I and III (d) I, II and III
ka

Solution: (a) Self explanatory

Problem 8: Formation of a complex in the solution can be detected by

(a) change in colour (b) change in solubility
lp

(c) change in pH (d) all are correct

Solution: (d)

Problem 9: Identify the complexes which are expected to be coloured

(a) [Ti(NO3)4 (b) [Cu(NCCH3)4]+ BF4
(c) [Cr(NH3)6]3+3Cl– (d) K3[VF 6]

Solution: (c)

Problem 10: Cu2+ is more stable than Cu+. This is due to

(a) extensive hydration of Cu2+ ion
(b) higher charge and smaller size of Cu2+ ion as compared to Cu+ ion
(c) both (a) & (b)
(d) none of these

Solution: (d)

[ 203 ]
Coordination Compounds and Organometallics

4.6 Organometallic Compounds

Organometallic compounds are those compounds which contain one or more metal-carbon
bonds. It may be noted that all the compounds containing Carbon and a metal atom are not
organometallic. We use this term for compounds which contain at least one M–C bond. For
example, an alkoxide such as (C 3 H7 O) 4 Ti is not considered to be an organometallic compound
because the organic group is bonded to Ti atom by oxygen and there is no Ti–C bond. On the
other hand, the compound C 6 H5 Ti(OC3 H7 )3 is an organometallic compound because it contain
a Ti–C bond (C 6 H5 –Ti) in the compound.
Ti (OC3H7)3
Ti (OC3H7)4
Not organometallic
(No C – Ti bond)
Organometallic
(C– Ti bond)

Classification of Organometallic Compounds.

JE

1. -bonded organometallics

2. -bonded organometallics
ES

1. -bonded organometallics. These compound contain metal-carbon covalent sigma bond.

The common example are :

(i) Grignard reagents, R–Mg–X where X = halogen, R = alkyl or aryl group.

an

CH3MgBr (methyl magnesium bromide), C2H5MgI (Ethyl magnesium iodide)

(ii) Diethyl zinc, (C2H5)2Zn. It was isolated in 1849 by Frankland.

ka

Here we represent Grignard reagent and diethyl Zinc by their empirical formulae. The
actual structures are more complicated. Diethyl zinc is monomeric in solution with C–Zn–
C coordination at Zn-atom.
lp

(iii) Trimethyl aluminium (CH3)3Al. It exists as a dimer with two methyl groups acting as
bridges between two Aluminium atoms.

Tri-aryl aluminium i.e., tri-phenylaluminium (C6H5)3 Al also exist as dimer.

(iv) Tetra ethyl tin, Sn(C2H5)4 and tetramethyl tin, Sn (CH3)4.

2. -bonded organometallics. These are usually formed by transition elements. The common examples
are:

(i) Zeise's salt, K[Pt Cl3(C2H4)].

It is written as K[PtCl3(2–C2H4)]. In these cases, the number of carbon atoms bond to

the metal is indicated by the Greek letter '' (eta)2 followed by a number. In this case,
Pt is bound to two carbon atoms and therefore, it is written as above

(ii) Ferrocene or bis (cyclopentadienyl) iron, Fe (5–C5H5)2.

[ 204 ]
Coordination Compounds and Organometallics

(iii) Dibenzene chromium, Cr(6–C6H6)2. Its structure is shown in Fig. (b).

Cr

(a) Ferrocene (b) Dibenzene chromium

Metal Carbonyls

In addition to the above two types of organometallics, there is another important class known as
metal carbonyl in which Carbon monoxide (CO) acts as ligand. These compounds contain both and
character. Some common metal carbonyls are :

(i) Nickel carbonyl, Ni(CO)4 (ii) Iron carbonyl, Fe(CO)5

JE

(iii) Chromium carbonyl, Cr(CO)6

Many carbonyl contains metal-metal bond also. For example, Mn2(CO)10

ES

Their structures are given below :

an
ka
(Ni(CO) 4 ] [Fe(CO) 5 ] [Cr(CO) 6 ] Mn2 (CO) 10

Bonding in Organometallic Compounds

lp

(a) Bonding in Metal Carbonyl: The bonding in metal carbonyls involves the following steps :

(i) There is a donation of lone pair of electrons of carbon (of CO) into the suitable empty
orbital of the metal atom. This is a dative overlap and forms a sigma M C bond.

(ii) There is a overlap involving donation of electrons from filled metal d-orbitals into vacant
anti-bonding molecular orbitals of CO. This results in back donation or back bonding.

(b) Bonding in Alkene Complexes: The bonding in alkene complexes involves the following
steps :

(i) The -electron density of alkene is donated into a vacant orbital of metal atom forming
alkene M bond.

(ii) back bonding resulting from the donation of filled d-orbital on the metal into the vacant
antibonding orbital of alkene. As a result of back bonding, the double bond character of
alkene is retained, though the bond becomes weak.

[ 205 ]
Coordination Compounds and Organometallics

Synthesis of organometallic Compounds

There are several methods of forming metal-carbon bonds. We are discussing here methods of some
common organometallic compounds.

1. Preparation of Organometallic Compounds:

(i) Grignard reagents are prepared by the slow addition of organic halide to a stirred
suspension of Magnesium turning (or metal) in the appropriate solvent in the absence of
air and moisture.
M + R–X Ether
 R–M–X

e.g. Mg + C2H5Br Ether

 C2H5MgBr
The reactivity of alkyl halide is RI > RBr > RCl and alkyl is more reactive than aryl.

(ii) Diethyl zinc is prepared by heating zinc with boiling alkyl halide in an inert atmosphere (CO2
or N2).
JE

2C2H5Br + 2Zn (C2H5)2Zn + ZnBr2

Diethyl zinc
ES

(iii) Tetra alkyl organometallics are prepared by treating metal halides with organometallic
reagents:
(a) nC4 H9Br + 2Li Dry
  n-C4H9Li + LiBr
ether
an

SnCl4 + 4C4H9Li (C4H9)4Sn + 4LiCl

Tetrabutyl tin

(b) C2H5 Br + Mg Dry

  C2H5MgBr
ether
ka

PbCl4 + 4C2H5MgBr (C2H5)4Pb + 4MgBrCl

Tetraethyl lead
lp

It can also be prepared by using an alloy

4C2H5I + Pb/Na (alloy) (C2H5)4Pb + 4NaI

2. Preparation of Metal Carbonyl –Complexes

(i) Metal carbonyls are prepared by the direct interaction of the finely divided metal and
carbon monoxide:

Ni + 4CO Ni(CO)4
200 C
Fe + 5CO   Fe(CO)5
high pressure

(ii) Metal carbonyls are prepared by a suitable metal salt and Carbon monoxide in the presence
of reducing agent.
2H
2
2CoCO3 + 8CO    CO2(CO)8 + 2Co2 + 2H2O
150  C, high pressure

[ 206 ]
Coordination Compounds and Organometallics

3. Preparation of –Complexes

(i) Zeise's salt is prepared by replacement of less strongly bond ligands such as halide ion
by alkene by directly heating ethylene and [PtCl4]2–

H2C = CH2 + K2[Pt Cl4] 

Zeise  K[(C2H4)Pt Cl3] + KCl
's salt

(ii) Ferrocene is prepared by the following reaction :

2C5H5MgBr + FeCl2   [(C5H5)2 Fe] + 2MgBrCl

Ferrocene

(iii) Dibenzene chromium is obtained by heating Benzene with Chromium vapours :

2C6H6 + Cr (vapour) (C6H6)2Cr

Applications of Organometallics
Organometallic compounds have very extensive applications :
JE

1. As homogeneous catalysis. Wilkinson's catalyst, (Ph3P)3RhCl is used as a homogeneous

catalyst in hydrogenation of alkenes.

2. As heterogeneous catalysis. Ziegler Natta catalyst (solution of TiCl4 and trialkyl aluminium)
ES

is used as a catalyst for polymerisation of olefins.

3. In organic synthesis, Organometallic compounds such as Organolithium, (R–Li),

Organomagnesium (R–Mg–X), Organocadmium (R2Cd) are used in many organic synthesis.
an

4. In metallurgical processes. Organometallic compounds are used in purification of metals.

For example, Nickel carbonyl is used in the purification of Nickel by Monds process.
ka

5. Tetraethyl lead is used as an antiknocking compound is gasoline (petrol).

6. Organosilicon compounds are used in medicines.

lp

7. Many organometallic compounds are finding applications in agriculture. For example ethyl
mercury chloride (C2H5 HgCl) is used as a fungicide.

8. Organosilicon compounds are used as polymers in silicon rubbers. Because of high thermal
stability, resistance to oxidation and chemical attack Silicon rubber are used in modern surgery
for the production of artificial body parts.

SAMPLE PROBLEMS 4.6 (MCQ)

Problem 1: Fe2(CO)9 is diamagnetic. Which of the following is the correct reason?
(a) One CO is present as bridge group
(b) CO is a -aceptor ligand
(c) CO can form -bond with Fe by back bonding’
(d) Metal-metal (Fe –Fe) bonding takes place

Solution: (d) Due to absence of unpaired electron.

[ 207 ]
Coordination Compounds and Organometallics

Problem 2: The value of n in the carbonyl (CO)n  Co  Co  (CO)n is

(a) 4 (b) 5
(c) 6 (d) 8
Solution: (a) Self explanatory
Problem 3: Among the following metal carbonyls, the C – O bond order is lowest is
(a) [Mn(CO)6]+ (b) [Fe(CO)3]
(c) [Cr(CO)6] (d) [V(CO)6]+
Solution: (d) Higher the extent of synergic bonding the bond length.

Problem 4: In Fe(CO)5, that Fe  COσ bond results by the overlap between filled sp hybrid orbital of
C-atom of CO molecule and vacant
(a) d2sp3 (b) sp3
3
(c) dsp (d) dsp2 hybrid orbital of Fe
Solution: (c) Self explanatory
JE

Problem 5: Which of the following carbonyls will have the strongest C – O bond?
(a) Mn(CO)6 (b) Cr(CO)6

(c) V(CO)6 (d) Fe(CO)5

ES

Solution: (a) Self explanatory

Problem 6: If the length of CO bond in carbon monoxide is 1.128Å, then what is the value of CO bond
length of Fe(CO)5?
an

(a) 1.15 Å (b) 1.128 Å

(c) 1.72 Å (d) 1.35 Å
Solution: (a) Self explanatory
ka

Problem 7: The correct structure of Fe(CO)5 is

(a) octahedral (b) tetrahedral
(c) square pyramidal (d) trigonal bipyramidal
lp

Solution: (d) Self explanatory

Problem 8: The non-existent metal carbonyl among the following is
(a) Cr(CO)6 (b) Mn(CO)5
(c) Ni(CO)4 (d) Fe(CO)5
Solution: (b) Self explanatory
Problem 9: The metal-carbon bond in metal carbonyls possesses
(a) only -character (b) only p-character
(c) both  and  character (d) ionic character
Solution: (c) Self explanatory
Problem 10: Which of the following is not considered as an organometallic compound?
(a) cis-plain (b) Ti (o-C2H5)4
(c) Zeise’s salt (d) Grignard reagent
Solution: (b) Self explanatory

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