CO-ORDINATION COMPOUNDS

Coordination compounds, terminologies, ligands and their

classification (mono, bi, tri, tetra,penta and hexa dentate ligands)
and ambidentate ligands, coordination number, nomenclature of
coordination compounds. Theories of structure and bonding
(Explanation for the formation of complexes by Werner’s Theory
taking cobalt amine complexes). EAN rule, Valence bond theory-
postulates, low spin and high spin complexes with examples
(cobalt and nickel-based complexes), limitations of VBT. Crystal
field theory (octahedral, tetrahedral and square planar
complexes). Isomerism-Structural: ionization, linkage, hydrate
and coordination isomerism with examples. Stereoisomerism
geometrical and optical isomerism in cobalt amine complexes.
 Coordination compounds

Coordination compound, any of a class of substances with

chemical structures in which a central metal atom is surrounded
by nonmetal atoms or groups of atoms called ligands, bound
via coordinate covalent bonds. Coordination compounds are also
referred to as coordination complexes.

Coordination compounds include such substances as Vitamin B12,

hemoglobin, chlorophyll, dyes, pigments and catalyst (Wilkinson's
Catalyst used in the hydrogenation of alkenes.) used in preparing
organic substances.
 Wilkinson's Catalyst
Vitamin B₁₂: Cobalamin
Ligands and their classification
Polydentate ligands
Ambidentate Ligand
Some ligands have the ability to bind to the
central atom via the atoms of two different
elements.
For example, the thiocyanate ligand (SCN) -
ion can bind to a ligand via the nitrogen
atom or via the sulfur atom. Such ligands
are known as ambidentate ligands.
It is important to note that these ligands are
capable of bonding to a central atom
through two different atoms, but only bonds
with one of them at a time. This type of
ligand also tends to be linear in geometry.
 Types of Coordination Complexes
•Cationic complexes: In this coordination, the sphere is a cation. For
example, [Co(NH3)6]Cl3

•Anionic complexes: In this coordination, the sphere is Anion. For

example, K4[Fe(CH)6]

•Neutral Complexes: In this coordination, the sphere is neither a cation

nor an anion. For example, [Ni(CO)4]

•Homoleptic complex: The complex consists of a similar type of

ligands. For example, K4[Fe(CN)6]

•Heteroleptic complexes: These consist of different types of ligands.

For example, [Co(NH3)5Cl]SO4
•Mononuclear complexes: In this coordination, the
sphere has a single transition metal ion. For example,
K4[Fe(CN)6]
•Polynuclear complexes: More than one transition metal
ion is present. For example,
 Nomenclature of Coordination compounds
• In naming the entire complex, the name of the cation is given
first followed by the anion.
Hexaamminecobalt(III) chloride [Co(NH3)6]Cl3.

lithium tetrahydrido aluminate(III) Li[AlH4]

 Nomenclature of Coordination compounds
•In the complex ion, the name of the ligand or ligands are named in alphabetical

order without regard to charge and precedes that of the central metal atom.
tetraammineaquachlorocobalt(III) chloride [CoCl(H2​O)(NH3​)4​]Cl2

• Ligand names generally end with 'o' / ‘ido' if the ligand is negative
('chlorido' for Cl- 'cyanido' for CN-, 'hydro' for H-)
• positive ligand ends with ‘ium’.
NH2NH3+ (hydrazinium), NO2+ (nitronium), NO+ (nitrosonium).
• unmodified if the ligand is neutral
('methanamine' for MeNH2).
• Special ligand names are 'aqua' for water, 'ammine' for ammonia, 'carbonyl'
for CO, 'nitrosyl' for NO.
Nomenclature of Coordination compounds

• A prefix (mono, di, tri, tetra, penta, hexa, etc.) indicates the
number of each ligand. If the name of the ligand itself contains
the terms mono, di, tri, eg triphenylphosphine, then the ligand
name is enclosed in parentheses and its number is given with
the alternate prefixes bis, tris, tetrakis instead.
NiCl2(PPh3)2 - dichloridobis(triphenylphosphane)nickel(II).
• If the complex ion is negative, the name of
the metal ends in ‘ate' for example, ferrate,
cuprate, nickelate, cobaltate etc.
• In polynuclear complexes, bridging ligands
are indicated by letter µ, before the ligand
name by hyphen
• The formula of charged complex ion is
written in square bracket and the charge is
indicated as a right superscript. [Co(H2O)6]
2+
, [FeF6]3-
• The formula of the entire coordination
entity whether charged or neutral is
indicated in square brackets. K4[Fe(CN)6],
[Ni(NH3)4]2+
• A Roman numeral or a zero in parentheses
is used to indicate the oxidation number of
the central metal atom.
Isomerism in Coordination compounds
Ionisation Isomerism

Same molecular formula but produces different ions in solvent.

Hydrate / Solvate Isomerism
Solvate isomers are a special case of ionisation isomerism in which compounds
differ depending on the number of the solvent molecule directly bonded to the metal
ion.
 [Co(H2O)6]Cl3
 [Co(H2O)5Cl]Cl2.H2O
 [Co(H2O)4Cl2]Cl.2H2O
 [Co(H2O)3Cl3].3H2O
Coordination Isomerism
Salts containing complex cation and anions may interchange ligands between
cation and anion forming coordination isomers.
Linkage Isomerism
Linkage isomerism is exhibited by coordination compounds having Ambidentate
ligands.
 Stereoisomerism
Coordination compounds which have the same molecular formula but have
different spatial arrangement are known as stereoisomers. These are further
divided into optical isomerism and geometrical isomerism.

Geometrical isomerism.

Geometrical isomerism is observed in heteroleptic complexes (complexes

with more than one type of ligand) due to different possible geometric
arrangements of the ligands.

This behaviour is mainly observed in coordination compounds having

coordination numbers equal to 4 and 6.
Optical Isomerism in Coordination Compounds

The isomer which forms a non-superimposable mirror image is

known as optical isomers or enantiomers, and they are of two types:

•The isomer that rotates plane-polarized light towards a clockwise

direction is the dextro or ‘d’ or ‘+’ isomer.

•The isomer that rotates plane-polarized light towards an anti-

clockwise direction is the leavo isomer or ‘l’, ‘-‘ isomer.

The equimolar mixture of ‘d’ and ‘l’ isomers is known as the racemic
mixture.
Werner’s Theory
Alfred Werner in 1898 proposed Werner’s theory explaining the structure of coordination compounds.
Werner was the first inorganic chemist to be awarded the Nobel Prize for chemistry in 1913.
Werner’s Experiment:
Werner explained the Structure and properties of following four complexes of Co (III) chloride with ammonia.
Werner’s Experiment (cont)

• Werner added the above four cobalt(III) complexes in table with an

excess silver nitrate solution. Which resulted in different amounts of
silver chloride precipitate.
• He concluded that in CoCl3.6NH3, 3Cl– ions react with 3 silver ion
form 3 silver chloride precipitates which act as primary
valency and 6NH3 molecules act as secondary valency. Thus in
modern term the compound is written as [Co(NH3)6] Cl3.
• Similarly, for CoCl3. 5NH3, 2Cl– ions act as primary valency, the
remaining 1Cl– and 5NH3 ions act as secondary valency. So the
compound is [Co(NH3)3Cl] Cl2
• For CoCl3.4NH3, 1Cl– is primary valency, 2Cl– and 4NH3 is
secondary valency. So the compound is [Co(NH3)5 Cl2] Cl
• For CoCl3.3NH3, all 3Cl– and 3NH3 ion act as secondary valency So
the compound is [Co(NH3)5 Cl3]
• He represents the primary valencies by dotted lines(…….) and
secondary valencies by solid line (—)
 Postulates of Werner’s Theory

 The central metal atom in the coordination compound exhibits two types of valency,
namely, primary and secondary valencies.
 Primary valencies are ionizable and are satisfied by the negative ions.(oxidation
state)
 Secondary valencies are non-ionizable. These are satisfied by negative ions or
neutral molecules(ligands). Also, the secondary valency is fixed for any metal.
(coordination number)
 The ions bounded by the secondary valency to the metal exhibit characteristic
spatial arrangements leading to geometrical shapes corresponding to different
coordination numbers. 2-linear, 4- tetrahedral or square planar, 6-ocathedral shapes.
 1. Primary Valency

• Primary valencies are those which a metal exhibits in the formation of simple
salts. e.g. CoCl3 , NaCl, CuSO4 etc.
• In modern terminology it represents the oxidation number of metal.
• e.g. the primary valencies of Co in CoCl3 is 3, and oxidation state +3
• Similarly, for NaCl, oxidation state of Na is +1, for CuSO4, oxidation state
of Cu is +2
• The primary valencies are ionizable.
• These are written outside the coordination sphere.
• These are non-directional and do not give any geometry to complex compound
• Example: [Co(NH3)6] Cl3, number of primary valencies 3, oxidation state +3
 2. Secondary Valency

• The secondary valency of metals is either by negative ions or neutral

molecules or both.
• In modern terminology it represents the coordination number of the
metal.
• Secondary valencies are written inside the coordination sphere.
• These are directional in nature and give definite geometry to the
complex.
• These are non-ionisable.
• Example: [Co (NH3)6]Cl3 coordination number is 6.
 Many coordination compounds are having same metal, same ligands

Compound1 CoCl3.6NH3 = [Co(NH3 )6 ](Cl3)

: Cl- is not in coordination sphere 3
free Cl- ions,[Co(NH3)6]3+
yellow colour

Compound2 CoCl3.5NH 3= [Co(NH3) 5Cl](Cl)2

:
2 free Cl- ions,[Co(NH3)5Cl]2+
Purple colour Cl

Compound3 CoCl3.4NH3 = [Co(NH3 )4C2l ]

: (Cl)
1 free Cl- ion,[Co(NH3)4Cl2]1+

Green Colour
Compound4 CoCl3.3NH3 = [Co(NH3 )3C3l ]
: No free Cl- ions
Limitations of Werner’s Theory
1. It fails to explain the magnetic, colour and optical properties shown by coordination compounds.
2. It failed to explain the reason why all elements don’t form coordination compounds.
3. It failed to explain the directional properties of bonds in coordination compounds.
4. This theory does not explain the stability of the complex
5. This theory could not explain the nature of complexes

Sidgwick’s Effective Atomic Number Rule

Central metal atom or ion accepts lone pairs of electrons donated by ligands till the total number
of electrons in metal becomes equal to the atomic number of the noble gas that follows the metal
in periodic table.
A complex is stable if the effective atomic number is equal to the atomic number of nearest inert
gas.
Complexes which obey EAN are diamagnetic
Limitations of Sidgwick’s Theory
1. Complexes like [Pt(NH3)2 Cl2] does not obey EAN rule and they are
diamagnetic.
2. It does not predict geometry of coordination compounds.
3. It does not explain spectral properties coordination compounds.
4. It does not distinguish between strong field and weak field ligands.
5. Accumulation of negative charge on the central metal atom in a complex must
lead to instability.
 Valence Bond theory
• This theory was proposed by Linus Pauling in 1931.

• It deals with electronic structure of the central metal atom/ion in its ground state, kind of
bonding, geometry, magnetic properties.

• According to this theory, when a complex is formed, the metal ion/atom provides empty
orbitals to the surrounding ligands. (coordination number)

• These empty orbitals hybridised to give hybrid orbital before participation in bonding and
the nature of hybridisation depends on the nature of metal and on the nature of approaching
ligand.

• A coordinate bond is formed by the overlap of a vacant metal orbital and filled ligand
orbitals.

• The geometry of complex depends upon the type of hybridised orbitals involved in bond
formation.
• Relation between the type of bond and the observed magnetic behaviour.

• The d orbital involved in hybridisation may inner d orbital or outer d orbital based on it
complexes formed can be either low spin complexes of high spin complexes.

• The complexes having unpaired non boding electrons get deflected in magnetic filed being
paramagnetic. Complexes without unpaired electrons don’t get deflected in magnetic filed
being diamagnetic.
 [NiCl4] 2-
• Z=28; outer electronic configuration [Ar] 3d84s2 ;
• oxidation state of Ni =2; coordination number = 4
• sp3 ; tetrahedral; 4 sigma coordinate bonds; paramagnetic.
• outer orbital; high spin complex
 [Ni(CN)4 ] 2-
• Z=28; outer electronic configuration [Ar] 3d84s2 ;
• oxidation state of Ni =2; coordination number = 4
• dsp2 ; octahedral; 4 sigma coordinate bonds; diamagnetic.
• inner orbital; low spin complex
 Hexaaminecobalt (III) chloride, [Co(NH3) 6]Cl3

• [Co(NH3) 6] 3+ ; Z=27; outer electronic configuration [Ar] 3d74s2 ;

• oxidation state of Co =3; coordination number = 6
• d2sp3 ; octahedral; 6 sigma coordinate bonds; diamagnetic.
• Inner orbital; low spin complex
 Potassium hexaflurocobaltate (III), K3[CoF6]

• Z=27; outer electronic configuration [Ar] 3d74s2 ;

• oxidation state of Co =3; coordination number = 6
• F ligand don’t force the pairing of electrons in the inner 3d orbital
• sp3d2 ; octahedral; 6 sigma coordinate bonds; paramagnetic.
• outer orbital; high spin complex
Limitations of Valence bond Theory
1. There's no explanation as to some ligand like F forming outer orbital complexes, where
as other ligands like NH3, CN forming inner orbital complexes.
2. It does not explain distorted octahedral geometry of six coordinated complexes of Cu 2+
ion.
3. It does not explain spectral properties coordination compounds (colour).
4. It does not explain variation in magnetic moments of complexes with temperature.
5. It fails to explain kinetic stabilities of coordination compounds.
 Crystal field theory (CFT)
• This theory was proposed by H. Bethe and van Vleck. Orgel. in 1952.
• Electrostatic interaction
• In this theory, ligands are treated as point charges in case of anions and dipoles in case of
neutral molecules.
• Central metal atom acts as cation
• The interaction of electrons of central metal ion and that of ligands are repulsive in nature.
• So, the degeneracy of five d orbitals of central metal ions in the complex is lost due to the
repulsive forces. The d-orbitals split into sets of different energy levels and is called crystal
field splitting.
The five d-orbitals are classified as
(i) Three d-orbitals i.e., dxy, dyz and dzx are oriented in between the coordinate axes and are called t 2g – orbitals.
(ii)The other two d-orbitals, i.e., dx2 - y2 and dz2 oriented along the x – y axes are called eg – orbitals.
Due to approach of ligands, the five degenerate d-orbitals split. Splitting of d-orbitals depends on the nature of the
crystal field. [The energy difference between t2g and eg level is designated by Δ and is called crystal field splitting
energy.
 Crystal field splitting in octahedral complexes
• In case of octahedral complexes, energy separation is denoted by Δo (where subscript 0 is for
octahedral).
• In octahedral complexes, the six-ligands approach the central metal ion along the axis of d x
2
-y
2
and
d z 2 orbitals.

• Energy of eg set of orbitals > energy of t2g set of orbitals.

• The energy of eg orbitals will increase by (3/5) Δo and t2g will decrease by (2/5) Δo.

• If Δo < P, the fourth electron enters one of the e g orbitals giving the configuration t 32g e1g. Ligands for
which Δo < P are known as weak field ligands and form high spin complexes.

• If Δo > P, it becomes more energetically favorable for the fourth electron to occupy a t 2g orbital with
configuration t42g eog. (where, P = energy required for electron pairing in an orbital).
• Ligands which produce this effect are known as strong field ligands and form low spin complexes.
Hexamminecobalt(III) chloride: Example of an octahedral
coordination complex.
 Crystal field splitting in tetrahedral complexes

In tetrahedral complexes, four ligands may be imagined to occupy

the alternate corners of the cube and the metal ion at the center of the
cube.

Energy of t2 set of orbitals > Energy of e set of orbitals.

The reason for this is due to poor orbital overlap between the metal and the ligand orbitals. The
orbitals are directed on the axes, while the ligands are not.
The difference in the splitting energy is tetrahedral splitting constant (Δ t), which less than (Δo)
for the same ligands:Δt =0.44 Δo

Consequentially, Δt is typically smaller than the spin pairing energy (P), so tetrahedral
complexes are usually high spin.
Crystal field splitting in tetrahedral complexes
Nickel carbonyl: 2-dimensional representation of tetrahedral
nickel carbonyl.
 Square Planar Complexes

In a square planar, there are four ligands.

The difference is that the electrons of the ligands are only attracted
to the xy plane leading to greatest interaction and therefore it has
higher energy.
The square planar complexes have the greatest crystal field
splitting energy compared to all the other complexes.
There are four different energy levels for the square planar are in
the order dx2-y2 > dxy > dz2 > dxz and dyz.
This arrangement is possible when the central metal ion has
d0, d8, or d10electron configuration, as these configurations have no
unpaired electrons and thus can accommodate more ligands.
The splitting energy (from highest orbital to
lowest orbital) is Δsp and tends to be larger
than Δo
Δsp=1.74Δo

Moreover, Δsp is also larger than the pairing

energy, so the square planar complexes are
usually low spin complexes.

Most of the square planar complexes are low

spin, with strong field ligands.
In [Ni(CN)4]2− ion complex, the valence shell
electronic configuration of Ni (o.s. +2) is 3d8.

Since CN– is a strong ligand, therefore, pairing of

two unpaired electrons of 3d orbitals takes place
resulting in a vacant d orbital.

This vacant 3d orbital gets hybridised with the

vacant 4s and two of 4p orbitals to give four dsp2
hybrid orbitals.

This leads to the formation of square planar

geometry and the magnetic moment is zero.
Hence, the complex is diamagnetic.