C OORDINATION C OMPOUNDS

Coordination compounds are the compounds in which the central metal atom is linked to a number of ions or neutral
molecules by coordinate bonds. Here the coordinate bonds results from the donation of lone pair of electrons by the neutral
molecules or ions to the central metal atom. . Coordination compounds may also be defined as those compounds which contain
complex ions. Ex- K4[Fe(CN)6], [Cu(NH3)4]SO4, Na[Ag(CN)2] etc.

→Types of Complexes

Thesearemainlyof3types.
Cationic Complex: - It carries net positive charge on it. Ex- [Co (NH3)6]3+, [Ni (NH3)6]2+
- -
Anionic Complex: - It carries net negative charge on it. Ex- [Ag (CN)2] , [Fe (CN)6]4 etc.
Neutral Complex: - It carries no net charge on it. Ex- [Ni(CO)4], [CO(NH3)3Cl3] etc.
→ Double Salt

When solutions of two or more salt are mixed in their simple molecular (stoichiometric) proportions (equimolar)
and then evaporated, then new crystals are separated out. The crystal is called double salt
Ex- Potash Alum- K2SO4Al2(SO4)3 24H2O Mohr’s Salt- FeSO4(NH4)2SO4. 6H2 O Carnallite- KCL. MgCl2. 6H2O

Double salts dissociates completely into simple ions when dissolved in water. Ex- KCL. MgCl 2. 6H2O → K++Mg2++3CL−+6H2O

Distinction between double salt and complex compounds.

Double Salt Complex Compounds
1. They exist in crystal lattices but breaks down to 1. They exist in solid state as well as in solution
simple ions when dissolved in water or in other because in the solution the complex ion does not
solution. dissociate.
2. Consists of two simple ions in equimolar 2. The constituent salts may not be present in
proportions. equimolar proportion.
3. The components do not lose their identity on 3. The components lose their identity on forming
forming double salt. complexes.
4. Here the metal ion exhibits their normal valency. 4. In complex compounds two types of valencies i.e.
primary and secondary valencies are seen.
5. They form ionic compound and do not have any 5. The complex compounds may or may not be ionic.
coordinate bond.
6. Double salts lose their identity in solution. 6. Coordination compounds retain their identity even in
the solution.
Important Terms More Frequently Used In Coordination Compounds
Coordination Entity: - A coordination entity/complex is defined as an electrical charged ion or neutral molecule which is formed
by the combination of a central ion or atom usually of a metal with one or more.
Ex- [Ni (NH3)6]2+ is formed by the combination of Ni2+cation with 6 neutral ammonia molecules. Here the species are enclosed
within square bracket “[ ]”.
Central Metal Atom/Ion: - The neutral metal atom or cations to which one or more neutral molecules or anions are attached by
coordinate bonds is called the central metal atom/ion.
Ex- [Ni (NH3)6]2+ here Ni2+ is the central ion.
Ligands:- The donor atoms, molecules or anions which donate a pair of electron to the metal atom or ion and form a coordinate
bond with the central metal are called as ligands.
Ex- [Ni (NH3)6]2+, NH3 molecules are the ligands.
• Ligands may be simple ions (Cl−), small molecules (NH3, H2O), and large molecules (ethylene diamine) or even macro
molecules such as protein.
• Thus ligands are Lewis bases whereas central atoms/ions is Lewis acids.
Types of Ligands
• When ligand contains one donor atom then it is called unidentate/monodentate .Ex- NH3, H2O, SO42−, CN etc.
• Polydentate/Multidentate Liagnds:- when ligands has two or more donor atoms which may coordinate simultaneously to the
metal atom is called polydentate ligand.
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Ligands with 2 donor sites = Didentate Ligands with 3 donor sites = Tridentate Ligands with 4 donor sites = Tetradentate
Ligands with 5 donor sites = Pentadentate Ligands with 6 donor sites = Hexadentate
Symmetrical and Unsymmetrical Ligands: - Ligands having same coordinating groups are called symmetrical ligands. Ex-
Ethylene Diamine (H2NCH2CH2NH2), Oxalate.
Ligands having different coordinating groups are called unsymmetrical ligands. Ex- glycinato ion.
Chelating Ligands: - These are multidentate ligands (having more than one donor sites) and they coordinate simultaneously with
the central metal forming ring compounds. Thus process is called chelation.
EX-

Chelate Effect: - Chelate compounds are more stable than ordinary complexes in which the ligand is monodentate. This
increases stability due to chelation is called chelate effect.
 Larger groups from unstable rings due to Steric Effect.
 Chelate complexes containing 5 to 6 membered rings are more stable.
 6 membered rings acquire stability when involves unsaturated ligands containing conjugated double bonds whereas 5
membered rings acquire stability when involves saturated ligands.
Ambidentate Ligands: - Ligands ng two or more different donor sites but only one of which is attached to a single metal at a given
time are called ambidentate ligands.
Ex- Thiocyanato (SCN–): M  SCN (M= Central Metal) Nitro: and Nitrito

Isothiocyanato (NCS–): M  NCS

Bridging Ligands: - The ligands that can simultaneously bind itself to more than one metal ion.Ex- OH —, Cl—, NH2—, etc. can be
both as monodentate and bridging ligands.
Co-ordination Number: – The total no. of coordinate bonds made by all the ligands with the metal is called coordination number
of the metal atom.
Ex- In [Cu(en)2]2+, the coordination no. of Cu2+ is 4. (Since each en links with 2 sites)
Coordination Sphere; – The central metal atom and the ligands directly attached to it are enclosed within square brackets “[ ]” is
called coordination sphere.
The ligands are always present within the “[ ]” are called co-center ion and these are ionisable.

Coordination Polyhedra: – The spatial arrangement of ligands

directly attached to central metal atom is called coordination
polyhedra. This spatial arrangement provides definite geometry to the
complex. M=Metal L=Ligands

Homoleptic and Heteroleptic Complexes: - Complexes in which

the central metal atom is bound to only one type of ligand (same

ligands) is called homoleptic complex. E.g. [Co (NH ) ]3+

3 6 ,

[Cr(CN) ]6 etc.

Complexes in which central metal atom is bound to move than one type of ligands are called Heteroleptic complex.

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E.g. [Co (NH ) Cl ]+ [Pt (NH ) Cl(NO )]
3 4 2 , 3 2 2 etc.

Oxidation Number/Oxidation State: - It is the charge held by the central metal atom when it is bonded to other ligands.

E.g. [Pt(CN) (H O) (NO )]2+

2 2 2

Since the overall complex has charge = +2

Thus,

K4[Fe(CN)6]

[Cr (NH ) ]Cl

3 6 3

[Co (NH3)4(H2O)Cl]

[Co (NH3)4(H2O)Cl]CL2

[Cr (NH3)6]3+:

[Ni (CN)4]2–

EAN Rule(Effective Atomic Number Rule): - It was proposed by Sidgwick. According to this rule, the effective atomic number
of the central metal atom or ion in a complex is equal to the total number of electrons present in the metal ion plus the number of
electrons donated to it by ligands.

Rules for Naming the Coordination Complexes

Order of naming ions: - +ve ions (cations) are named 1st, followed by (-ve) ions. The naming starts with small letter and the
complex ion is written in one word.

Naming of Ligands

 (—) organic/inorganic ligands end in ‘—o’.

 (+) ligands end with ‘—ium’.
 Neutral ligands have no special ending.
 Organic ligands – organic free radicals are given their own names.
E.g. CH3– Methyl, C2H5– Ethyl, C6H5– Phenyl etc.

Ligands Formula Charge Donor Atom Naming

a) Unidentate
Cyanide Ion CN— —1 C Cyano
Halide Ion X—(F–, Cl–, Br–, I–) —1 X Halido(Fluorido, Chlorido, bromido,
Iodido)
Nitro NO2— —1 N Nitro
Nitrite Ion ONO— —1 O Nitrito
Hydride Ion H— —1 H Hydrido
Nitrate Ion NO3— —1 N Nitrato
Hydroxide Ion OH— —1 O Hydroxido
Amide Ion NH2 —1 N Amido

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Thioyanate Ion SCN— —1 S Thioyanato
Isothiocyanate NCS— —1 N Isothiocyanato
Acetate Ion CH3COO— —1 O Acetato
Oxide Ion O2— —2 O Oxo
Poroxide Ion O22— —2 O Peroxo
Sulphide Ion S2— —2 S Sulphido
Sulphite Ion SO32— —2 S Sulphito
Sulphate Ion SO42— —2 S Sulphato
Thiosulphate Ion S2O32— —2 S Thiosulphate
Carbonate Ion CO32— —2 O Carbonate
Imide Ion NH2— —2 N Imido

Ligands Formula Charge Donor Naming

b) Didentate Atom
Oxalate Ion (OX) —2 Two ‘O’ Oxalato
atoms

Acetylacetonate(acac) —1 Two ‘O’ Acetyl–

atoms acetonato

Glycinate Ion (gly) —1 One ‘N’ Glycinato

atom and
one ‘O’
atom

Dimethyl Glyoxime —1 one ‘O’ and Dimethyl–

ion (dmg) one glyoximato

‘N’ atom

c) Pentadentate
Ethylenediamine —3 Three ‘O’ Ethylendia–
triacetate (edta3–) and two ‘N’ mine Triacetato
atom

d) Hexadentate
Ehtylenediaminetetreaacetate —4 Two ‘N’ Ethylene–
ion atoms and diamine
(edta4–) four ‘O’ tetraacetato
atoms

Neutral Ligands
Ligands Formula Charge Donor Atom Naming
a) Unidentate
Ammonia (NH3) 0 N Ammine
Water H2O 0 O Aqua

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Nitiric Oxide NO 0 N Nitrosyl
Carbonmonoxide (CO) 0 O Carbonyl
Thiocarbonyl (CS) 0 S Thiocarbonyl
Phosphine PH3 0 P Phosphine
Thiourea H2NCSNH2 0 S Thiourea
Pyridine C5H5N 0 N Pyridine

b) bidentate 0 Two ‘N’ atoms Ethylene Diamine

Ethylenediamine
(en)

2,2-Diapyridyl O Two ‘N’ atoms Dipyridyl

(dipy)

Ortho-phenathorline O Two ‘N’ atoms Phenathroline

d) Tetradentate 0 Four ‘N’ atoms TriethyleneTetramine

TriethyleneTetratetramine
(trien)

c) Tridentate 0 Three ‘N’ Diethylenetriamine

DiethyleneTriamin atoms
e (dien)

Positive Ligands

Hydrazinium Ion NH2—NH3+ +1 N Hydrazinium

Nitrosonium Ion NO+ +1 N Nitrosonium
Nitronium Ion NO2+ +1 N Nitronium
Naming the complex ion: -
i) When same type of simple ligands then use di, tri, tetra etc. before the name of the ligands.
ii) When more than one same type of a polydentate ligand is there, they use bis, tris etc.
iii) For organic ligands like triphenyl phosphine, to avoid confusion we use bis, tris etc.
iv) Positive are named first followed by –veions(+ve ion refers to the counter ions).
v) Number and name of the ligand is written first followed by the central metal atom.
vi) The name of the central metal atom is followed by its oxidation number written within parenthesis in Roman numeral.
vii) If ligands of same kind or same type (i.e. more than one anionic/neutral ligands) are present then naming is done
alphabetically or depending on the bulkier. (less bulkier are named 1st)
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viii) if the complex is anion then the name os the metal ends with –ate but there will be no change for neutral ligands.

e.g. [Cr (NH ) ]Cl ⇒ Oxid no. of Cr + 0 +3(-1) = 0 ⇒ Oxid no. of Cr = +3

3 6 3
n n

So, NH3 being monodentate type, the name is hexaamminechromium (III) chloride.

[Co (NH ) Cl ]— Triamminetrichloridocobalt (III)

3 3 3

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Writing Formula of a Complex

i) The simple ion (counter ion) whether cation or anion behaves like free ion and carries usual charge as one radical.
ii) Charge on complex ion (coordination entity) is done as
Charge on complex ion (x) =Oxidn state of metal + Charges on the ligands (with sign)
iii) Since a molecule of the coordination compound as a whole is neutral, total positive charge must be equal to total negative
charge. The cations and anions are multiplied by such constants so that charge becomes equal. Then constant represent the number
of each type of ions.
E.g. Tetraamineaquachloridecobalt(III)chloride
As after the name of the ligand there is chloride which is anionic type; so the complex is cationic Arranging the ligands in

alphabetical order after the metal; [Co (NH ) (H O)Cl]x

3 4 2

x = oxid state of (Co) + charge on ligand

n

= +3+0+0+(-1) = +2 ⇒ Charge on the complex is +2

As charge on the complex is +2; two Cl— ions are required for neutralizing it. Anions are present on the right of the [ ].

So, [Co (NH ) (H O)Cl]Cl

3 4 2 2

Werner’s Theory
Alfred Werner, a Swiss chemist studied the bonding in coordination compounds in 1972.
Postulates

i) Metals possess 2 types of valencies i.e. primary (10) or principal or ionisablevalency and secondary (20) or non-
ionisablevalency.
Primary Valency: - Here metal exhibits simple salts and are ionisable. It is referred to as oxidation number. E.g. CuSO 4 →
Cu2+⇒ 10valency is 2.
Secondary Valency: - It is satisfied by neutral molecules or negative ions. It is equal to coordination number of the metal.
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 ii) Every metal atom has tendency to satisfy both primary and secondary valencies.
iii) Ligands satisfying secondary valencies are directed towards fixed positions(directional in nature); these given definite
geometry to the complex.

iv)Primaryvalencies are non-directional.

v) Every metal atom has fixed number of secondary valencies or coordination number.
10valencies→ Ionic bonds, 20valenices → coordinate bonds.

vi) Primary valency is donated by dotted lines and secondary valency is donated by arrow .

Composition of Ions/AgCl precipitated on adding AgNO3 Secondary Valencies

Complex
PtCl4.6NH3 4 AgCl 6
PtCl4.5NH3 3 AgCl 6
PtCl4.4NH3 2 AgCl 6
PtCl4.2NH3 No ions formed 6
CoCl4.Cl2NH3 1 AgCl 6
PtCl4.2HCl No ions formed 6
PdCl4.4H2O 2 AgCl 4
So, ions precipitated out ⇒ those are primary valencies since the 20valencies are non-ionisable, so the rest ligands represent
20valency.
Limitations of Werner’s Theory

 Could not explain why certain elements form coordination compounds and not at all.
 Cannot explain why coordination entities has definite geometry(bonding and hybridization ).
 It given no idea regarding the magnetic and optical properties, exhibited by the compounds.

Valence Bond Theory This theory was extended to coordination compound by Pauling in 1931.
Postulations
i) The metal – ligand bond arises by donation of pairs of electrons by ligands to the metal atoms/ions. Thus metal should have
vacant space to accommodate the accepted electrone and ligand should have capability to donate electron or should contain lone
pair electron .

ii) Metal acquires electrons in its vacant hybrid orbitals.

iii) The orbitals used in hybridation may be inner (n—1)d or outer nd-orbitals, s-orbitals and p-orbitals.
iv) The number of orbitals present in the metal atom/ion is equal to the coordination number for accepting electrons from ligands.
Thus the bonding between metal and ligand is purely covalent
v) Presence of unpaired electrons gives rise to paramagnetism and paired electrons given rise to diamagnetism.

A) Octahedral Complexes I
Inner-orbital Complexes:-

1.[Cr (NH ) ]3+: The oxidation no of Cr is +3 (octahedral complex).Cr has electronic configuration; 3d 4s
3 6
5 1

Cr is in ground state

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Cr3+ excited state

Since three unpaired electrons are present, hence is paramagnetic.

2.[Fe (CN) ]3–: Oxidation number is +3 Fe = 3d 4s

6
6 2

Inner orbital complexes are mostly diamagnetic or have lesser number of unpaired electrons.

Outer Orbital Complexes: - These complexes use nd-orbitals for hybridization. They have large number of unpaired electrons.
So they form high spin complexes.

[Co F ]3– = Oxid no is +3.

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n
Co = 3d74s2

B) Tetrahedral Complexes

Ni(CO)4: Ni= 3d84s2 ; oxidation state = 0

Hybrdized Sp3

lC) Square Planar

[Ni (CN) ]2– Ni is in +2 oxidation state.

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Ni in grounded state

Ni2+ ion

dSp2 hybridized orbital of Ni2+

It appears to have Sp3 hybridization but actually follows dSp2 hybridization (Square planar).
Drawbacks of VBT

 It cannot explain why metal ion in a particular oxidation state is low spin (inner orbital complex) while in other
complexes having same oxidation state is high spin (outer orbital complex).
 The magnetic behavior predicted by VBT sometimes do not match with the experimental data.
 It cannot explain why complexes exhibit color.
 It cannot exactly explain the thermodynamic and kinetic stability
of complexes.

Crystals Field Theory (CFT) It was proposed by Hans Bethe

(1929) and John Van Vleek (1932).
Postulates

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  It consders the metal ligand bond to be ionic, arising from electrostatic interactions between the metal atom/ion and the
ligands.
 Each metal atom or ion is a point +ve charge and ligand is point of negative charge and their arrangement around the
metal atom is such that the distance between these negative point are maximum and repulsion is minimum.
 In a free transition metal ion, all the five -d-orbitals have equal energies and degenerate, provided they produce a
spherical symmetric field around the central metal atom.
 For an un-symmetrical field, the degeneration breaks and the orbitals splits.

The 5-d-orbitals are

CFT for Octahedral Complexes

As the ligand approaches the metal ion, there arises repulsion between the ligands and the d-orbitals. This raise the energy of the
orbital.dx2–y2 and d22 having their lobes axis feel maximum repulsion from ligands as they approach directly while dxy, dyz and
dzx being present in between the axis undergo minimum repulsion. Thus dx2–y2 and dz2 are raised in energy called Cg orbitals(two
fold degenerate) while energy called dxy, dyz and dzx are in lower energyforming t2g orbitals.

CFT for Tetrahedral Complexes

Here the crystal field splitting is just the reverse of that of octahedral field. The distance of separation between the two sets of
splitted orbitals is ∆t. ∆t < ∆0; thus tetrahedral complexes mostly form high spin Complexes.

Spectrochemical Series
The arrangement of ligands in increasing order of their filed strength is called spectrochemical series.
I–<Br–<S2–<SCN–<Cl–<F–<OH–<C2O42–<O2–<H2O <NCS–<NH3<CN <NO2–<CN <CO
Weak field ligands —————————————————————→ Storng field ligands
In order of ∆0
The value of ∆0is compared with energy required for pairing of electrons in a single orbital (P) or pairing energy.
If ∆0< P the 4th electron enters eg as distance of separation is small ⇒ high spin complexes are formed and the ligands are weak
field ligands.
 If ∆0> P the 4th electron enters the t2g orbital resulting in pairing ⇒ low spin complexes are formed. This is seen for strong field
ligands.

Limitation of CFT
 As it considers ligands as point charges, the anionic ligands exert greater splitting effect but anionic ligands are present at
lower end of the series.
 It considers metal ligand bond to be ionic and does not considers the covalent characters of the bond.

Stability of Complexes
It may be defined as the measure of resistance to replacement of a ligand by some other ligand.

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 As the dissociation involves equilibrium between dissociated and the unassociated components, the equilibrium constant
is called instability constant or dissociation constant
.

If we take the formation of the complex then the equilibrium constant is called stability constant ( β ).
So, β n = K1 x K2 X K3 X ……………x Kn
Factors Affecting Stability of Complexes
Nature of Central Metal
Greater the charge smaller the size of metal atom/ion, more is the stability of the complex.
So, Cu2+> Ni2+> Co2+> Fe2+> Mn2+ (Irving Wiilliam Order)
Basicity of Ligands
More the basicity, more easily it can donate electron parts and thus stable complexes are formed. Anionic ligands form stable
complexes than neutral ligands. Chelate effect provides better stability to the complex.
Colors of Coordination Compounds
Transition metal complexes have distinctive colors when light passes through such complexes, some of the wave lengths are
absorbed and rest are reflected back. The color of the complex is complementary to that absorbed. The color of the complex can
be explained by CFT.
In the absence of ligand, crystal field splitting does not occur and the substance is colorless.
Colour is due to presence of unpaired electrone and absorption of visible ligfht for d to d transition

[ ]
E.g. Ti (H2O)6 Cl3————————————————→ Colorless (H2O molecules are removed)
Anhydrous CuSO4 ————————————————→ CuSO4 . 5H2O
(white) (blue)

[Ni (H O) ]2+ , with the replacement of H O, by en, series of reactions occur followed by color charge.
In complex 2 6 2

[Ni (H O) ]2+ + en (aq) —————————————→ [Ni (H O) (en)]2+ + 2H O

2 6 (aq) 2 4 (aq) 2

[Ni (en) ]2++ 2H O ←—————————————[Ni (H O) (en) ]2+ + 2H O(violet

3 2 2 2 2 (aq) 2

In [Ti (H O) ] (violet) the complex absorbs yellowish green color and excitation of
3+
(Blue) 2 6
electron occurs from ground to excited state.
Isomerism of Coordination Compounds:- When two or more compounds have same molecular formula but differ in their
physical and chemical properties then they are called isomers and the phenomenon is called isomerism.

Isomerism

Stereoisomerism Structural Isomerism

Geometrical Ionisahon

Optical Linkage

Hydrate or Solvate

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 Coordination
Stereoisomerism
When two or more compound have same formula but differ in the spatial arrangement of ligands around the central metal atom,
then it is called stereoisomerism.
It is seen in coordination no = 4 (square planar complex)
= 6 (Octaorbital Complex)

Geometrical Isomerism
 Its first type is Cis-trans isomerism.
 When same ligands are present on same side having minimum angle between them, it is called cis form while same
ligands are present on opposite sides having iso angle between them are trans.

Facial (Fac) and meridonal (mer) isomerism when same type of ligands in an octahedral complex constitutes a face of the
octahedron it is called facial isomer.

When these same type of ligands are present in the meridian of the polyhedron it is called meridonal isomers.

Optical Isomerism

This is seen in optically active substances and it is related to mirror image relationship. It represents the isomerism where the
mirror image of the substance is non-superimposable on it.

For CN26: -Square planar complex do not show this type of isomerism as they possess the plane of symmetry. But tetrahedral
complexes containing unsymmetrical ligands can show such isomerism.

For C. N26

E.g.[Co (en) Cl ]+ 2 2

Structural Isomerism

Ionisation Isomerism: - Compounds having same formula but their capacity to liberate ions in solution is different. This arises due

to the presence of different types of counter ions. E.g [Co (NH ) SO ]Br— releases Br
3 5 4
—
ions with AgNO3(Pale yellow ppt)

[Co (NH ) Br]So → releases SO

3 5 4 4
2–
ion white ppt BaSO4

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Linkage Isomerism: - It is mostly shown by ambidentate ligands as they have same formula but vary only with the type of donor
atom linked with the metal at a particular time.

E.g.

Coordination Isomerism: - It arises when there is a cationic complex and an anionic complex. In this isomerism there is complex
exchange of ligands present in both the complexes

.E.g

.Hydrate/Solvate Isomerism: - The complexes have same molecular formula but differ in the number of water molecules present
inside and outside the coordination there. i.e. they differ in the amount of water molecules released.

Applications of Coordination Compounds: -

1) In Analytical Chemistry ---- During qualitative analysis in salt analysis, the presence of a number of basic radicals is
confirmed by converting them into suitable complexes having definite colors.
2) In quantitative (estimation) During gravimetric analysis amount of metal present in a complex is determined by converting it
into an insoluble complex.In volumetric analysis various metal ions react with polydentate ligands and is useful for estimation .3)
In Metallurgy Various noble metals like gold, silver are extracted from their ores by the help of various coordination complexes
4) In Purification of Metals: - Various metals are purified by forming their metal carbonyls followed by their
decomposition .5) In Industry: - In various industrial process, coordination compounds are used at catalyst. They are also used
in electroplating and photography, in dyes or pigments.
6) In Medical Field: - The platinum complex cisplatin has been useful in treatment of cancer, EDTA is used for treatment of load
poisoning etc.
7) In Agriculture: - To prevent the infection of young plant, the seeds are treated with organometallic, like ethylmercurychloride
which are also coordination complexes.
8) In Biological Systems: -

 Chlorophyll, the green pigment which is responsible for preparation of food by plants in anMg–complex.
 Hemoglobin, red pigment of blood that acts as the oxygen carrier is a coordination compound of iron.
 Vitamin-B12, chemically called as cyanocobalamine is antiperniciousanaemia factor is a coordination compound of
cobalt.

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