Werner's Theory of Coordination Compounds &

Definition of Important Terms in Coordination Compounds

 Coordination Compounds − Complex compounds in which transition metal atoms are bound
to a number of anions or neutral molecules
Postulates of Werner’s Theory of Coordination Compounds
 In coordination compounds, there are two types of linkages (valences) − primary and
secondary.
 The primary valences are ionisable, and are satisfied by negative ions.
 The secondary valences are non-ionisable, and are satisfied by negative ions or neutral
molecules. The secondary valence is equal to the coordination number of a metal, and remains
fixed for a metal.
 Different coordination numbers have characteristic spatial arrangement of ions or groups
bound by the secondary linkages.
Such spatial arrangements are called coordination polyhedra. The species within the square
brackets are called coordination entities or complexes, and the ions outside the square
brackets are called counter ions.
Difference between a Double Salt and a Complex
 In water, a double salt dissociates completely to give simpler ions. Examples of double salt:
carnallite (KCl.MgCl2.6H2O), Mohr’s salt [FeSO4.(NH4)2 SO4.6H2O]
 Complex ions do not dissociate further to give simpler ions; for example, [Fe(CN) 6]4−,
[Fe(C2O4)3]3−.
Definition of Important Terms in Coordination Compounds
 Coordination Entity
o Constitutes a central metal atom or ion bonded to a fixed number of ions or molecules
o Example: [CoCl3(NH3)3] is a coordination entity
 Central Atom or Ion
o
The atom or ion to which a fixed number of ions/groups are bound in a definite
geometrical arrangement around it in a coordination entity
o
Example: Ni2+ in [NiCl2(H2O)4] and Fe3+ in [Fe(CN)6]3−
 Ligands
Ions or molecules bound to the central metal atom or ion in a coordination entity
o Didentate

 Polydentate
 Ambidentate
(Can bind through two different atoms)

 Coordination Number
o Number of ligand-donor atoms bonded directly to the metal
o Example: The coordination number of Pt and Ni in [PtCl 6]2− and [Ni(NH3)4]2+ are 6 and
4 respectively.
 Coordination Sphere
o The central atom or ion and the ligands attached to it are enclosed in square brackets,
which are collectively known as the coordination sphere.
o Example: In the complex K4[Fe(CN)6], the coordination sphere is [Fe(CN)6]4−.
 Coordination Polyhedron
o The spatial arrangement of the ligand atoms which are directly attached to the central
atom or ion
o Example: Octahedral, square planar, tetrahedral

 Oxidation Number of Central Atom

o The charge it would carry if all the ligands are removed along with the electron pairs
that are shared with the central atom
o Example: Coordination number of copper in [Cu(CN) 4]3− is 1.
 Homoleptic and Heteroleptic Complexes
o
Homoleptic − Complexes in which the metal is bound to only one kind of donor group.
 Example: [Co(NH3)6]3+
o
Heteroleptic − Complexes in which the metal is bound to more than one kind of donor
groups. For example: [Co(NH3)4Cl2]+

Nomenclature of Coordination Compounds

Formulas of Mononuclear Coordination Compounds
The following are the rules for writing the formulas.
 The central atom is listed first.
 The ligands are then listed in the alphabetical order.
 Polydentate ligands are also listed in the alphabetical order. In the case of abbreviated
ligands, the first letter of the abbreviation is used for determining the position of the ligands in
the alphabetical order.
 The formula of the entire coordination entity is enclosed in square brackets. Ligand
abbreviations and formulas for polyatomic ligands are enclosed in parentheses.
 There should be no space between the ligands and the metal within a coordination sphere.
 For the charged coordination entity, the charge is indicated outside the square brackets, as a
right superscript, with the number before the sign. Example: [Fe(CN) 6]3−, [Cr(H2O)6]3+, etc.
 The charge of the cation(s) is balanced by the charge of the anion(s).
Naming of Mononuclear Coordination Compounds
The following rules are followed while naming coordination compounds.
 The cation is named first in both positively and negatively charged coordination entities.
 The ligands are named in alphabetical order before the name of the central atom/ion.
 Names of the anionic ligands end in −o and those of neutral and cation ligands are the same.
[Exceptions: aqua (H2O), ammine (NH3), carbonyl (CO), nitrosyl (NO)]
 To indicate the number of the individual ligands, the prefixes mono−, di−, tri−, etc., are used.
If these prefixes are present in the names of ligands, then the terms −bis, −tris, −tetrakis,
etc., are used. For example, [NiCl2(PPh3)2] is named as
dichlorobis(triphenylphosphine)nickel(II).
 Oxidation state of the metal is indicated by a Roman numeral in parentheses.
 If the complex ion is cation, then the metal is named as the element. For example, Fe in a
complex cation is called iron and Pt is called platinum.
 If the complex ion is anion, then the metal is named with ‘−ate’ ending. For example, Co in a
complex anion, [Co(SCN)4]2− is called cobaltate.
 The neutral complex molecule is named as the complex cation.
IUPAC name of some coordination compounds are as follows:
[Ni(CO)4] − Tetracarbonlynickel(0)
 [Co(NH3)3(H2O)3]Cl3 − Triamminetriaquachromium(III) chloride
[Pt(NH3)2Cl(NO2)] − Diamminechloridonitrito-N-platinum(II)
[CoCl2(en)2]Cl − Dichloridobis(ethane-1,2-diammine)cobalt(III) chloride
K2[Zn(OH)4] − Potassium tetrahydroxozincate(II)

Isomerism in Coordination Compounds

 Stereoisomers have same chemical formula and chemical bonds, but have different spatial
arrangement.
 Structural isomers have different chemical bonds.
Geometrical Isomerism
 Arises in heteroleptic complexes due to different possible geometrical arrangement of ligands
 Generally found with compounds having coordination numbers 4 and 6
 Square planar complex of formula [MX2L2] (X and L are uni-dentate) exhibits geometrical
isomerism − cis-isomer and trans-isomer.
o Example − Geometrical isomers of Pt(NH 3)2Cl2

 Octahedral complex of formula [MX2L4] also exhibits geometrical isomerism.

o
Example − Geometrical isomers of [Co(NH3)4)Cl2]+

 Octahedral complex of formula [MX2 (L − L)2] exhibits geometrical isomerism, where L−L is a
bidentate ligand. [e.g., NH2 CH2 CH2 NH2(en)]
 o Example − Geometrical isomers of [CoCl2 (en)2]

 Octahedral complexes of type [Ma3b3] exhibit another type of geometrical isomerism − facial
(fac) isomer and meridional (mer) isomer.
o Example − [Co(NH3)3(NO2)3]

o Facial (fac) isomer − Three donor atoms of the same ligands occupy adjacent positions
at the corners of an octahedral face.
o Meridional (mer) isomer − When the positions of the donor atoms are around the
meridian of the octahedron
Optical Isomerism

Optical isomers (also called enantiomers) − Mirror images that cannot be superimposed on
one another

Chiral − Molecules or ions that cannot be superimposed

Two forms − dextro (d) and laevo (l)

d-isomer rotates the plane of polarised light to the right and l-isomer rotates it to the left.

Example − ‘d’ and ‘l’ isomer of [Co(en)3]3+

 → Only cis isomer shows optical activity.

Linkage Isomerism
 Arises in the compound containing ambidentate ligand (which can ligate through two different
atoms)
 Example: Thiocyanate ligand (NCS−) can bind through nitrogen to give M−NCS or through
sulphur to give M−SCN.

 also exhibits two forms:

 Red form − Nitrite ligand binds through oxygen (−ONO).
 Yellow form − Nitrite ligand binds through nitrogen (−NO 2).
Coordination Isomerism
 Arises from the interchange of ligands between cationic and anionic entities of different metal
ions present in the complex

 Example −
Ionisation Isomerism
 Arises when the counter ion in the complex salt is itself a potential ligand and can displace a
ligand, which can then become the counter ion

o Example −
Solvate Isomerism
 Known as ‘hydrate isomerism’ when water is involved as a solvent
 Similar to ionisation isomerism
 Solvate isomers differ by whether or not a solvent molecule is directly bonded to the metal ion
or merely present as free solvent molecules in the crystal lattice.

 Example − (violet) and (grey green)

Valence Bond Theory and its Limitations & Magnetic

Properties of Coordination Compounds
Valence Bond Theory
 The metal atom or ion under the influence of ligands can use its (n−1)d, ns, np or ns, np, nd
orbitals for hybridisation, to yield a set of equivalent orbitals of definite g eometry such as
octahedral, tetrahedral, square planar, and so on.

Coordination number Type of hybridisation Distribution of hybrid

orbitals in space

4 sp3 Tetrahedral
4 dsp 2
Square planar
5 sp d 3
Trigonal bipyramidal
6 sp d 3 2
Octahedral
6 d sp
2 3
Octahedral

 These hybridised orbitals are allowed to overlap with ligand orbitals that can donate electron
pairs for bonding.
 Octahedral Complexes
o The hybridisation involved can be d2sp3 or sp3d2.
o Inner-orbital or low-spin or spin-paired complexes: Complexes that use inner d-
orbitals in hybridisation; for example, [Co(NH3)6]3+. The hybridisation scheme is shown
in the following diagram.

o Outer-orbital or high-spin or spin-free complexes: Complexes that use outer d-orbitals

in hybridisation; for example, [CoF6]3−. The hybridisation scheme is shown in the
following diagram.

 Tetrahedral Complexes
 o
The hybridisation involved is sp3
o
Example: [NiCl4]2−
o
The hybridisation scheme is shown in the following diagram.

 Square planar Complexes

o
The hybridisation involved is dsp2
o
Example: [Ni(CN)4]2−
o
The hybridisation scheme is shown in the following diagram.

Magnetic Properties of Coordination Compounds

 Complexes with unpaired electron(s) in the orbitals are paramagnetic.
 Complexes with no unpaired electron(s) in the orbitals (i.e., all the electrons are paired) are
diamagnetic.
 Example: [MnCl6]3−, [FeF6]3− and [CoF6]3− are paramagnetic. It can be explained on the basis
of the valence bond theory. These coordination compounds are outer-orbital complexes with
sp3d2 hybridisation, and are paramagnetic containing four, five and four unpaired electrons
respectively.
On the other hand, [Co(C2O4)3]2− is diamagnetic. According to the valence bond theory, it is an
inner-orbital complex involving d2sp3 hybridisation, with no unpaired electron(s), and is
diamagnetic.
Limitations of Valence Bond Theory
 A number of assumptions are involved.
 Quantitative interpretation of magnetic data is not given.
 The exhibition of colour by coordination compounds is not explained.
  The thermodynamic or kinetic stabilities of coordination compounds are not quantitatively
interpreted.
 Whether a complex of coordination number 4 is tetrahedral or square planar cannot be exactly
predicted.
 Weak and strong ligands cannot be distinguished.

Crystal-Field Theory
 An electrostatic model which considers the metal−ligand bond to be ionic, which arises purely
from the electrostatic interaction between the metal ion and the ligand
 Ligands are treated as point charges in the case of anions, or dipoles in the case of neutral
molecules.
 The five d-orbitals in an isolated gaseous metal atom/ion are degenerate (i.e., have the same
energy).
 Due to the negative fields of the ligands (either anions or the negative ends of dipolar
molecules), the degeneracy of the d-orbitals is lifted, resulting in the splitting of the d-orbitals.
Crystal-Field Splitting in Octahedral Coordination Entities
Crystal-field splitting is the splitting of the degenerate energy levels due to the presence of ligands.
 The splitting of d-orbitals in an octahedral crystal-field is shown in the given figure.

o The and orbitals (i.e., eg set), which point towards the axes along the
direction of the ligand, will experience more repulsion, and will be raised in energy.
o The dxy, dyz and dxz orbitals (i.e., t2g set), which are directed in between the axes, will
be lowered in energy relative to the average energy in the spherical crystal-field.
o The energy separation is denoted by Δo (the subscript ‘o’ is for octahedral)
o The energy of two eg orbitals will increase by (3/5)Δo, and that of three t2g orbitals will
 decrease by (2/5)Δo.
 Spectrochemical series
Ligands are arranged in a series in the increasing order of the field strength as follows:

 Ligands for which Δo (crystal-field splitting) < P (pairing energy), are called weak-field ligands,
and form high-spin complexes.
 Ligands for which Δo (crystal-field splitting) > P (pairing energy), are called strong-field
ligands, and form low-spin complexes.
Crystal-Field Splitting in Tetrahedral Coordination Entities
 The splitting of d-orbitals in a tetrahedral crystal field is shown in the given figure.

 Δt = (4/9) Δo
 The orbital-splitting energies are not sufficiently large for forcing pairing, and therefore, low-
spin configurations are rarely observed.
Colour in Coordination Compounds
 The colour of the coordination compounds is attributed to d−d transition of electrons.
o For example, the complex [Ti(H2O)6]3+ is violet in colour, which is due to d−d transition
(shown in the figure)

o The energy of yellow-green region is absorbed by the complex, and then, the electron

gets excited from t2g level to the eg level, i.e.,

 The relationships between the wavelength of light absorbed and the colour observed in some
coordination entities are listed in the given table.
 Coordination Wavelength of light Colour of light Colour of
entity absorbed (nm) absorbed coordination entity

[CoCl(NH3)5]2+ 535 Yellow Violet

[Co(NH3)5(H2O)]3+ 500 Blue-green Red

[Co(NH3)6]3+ 475 Blue Yellow-orange

[Co(CN)6]3− 310 Ultraviolet Pale yellow

[Cu(H2O)4]2+ 600 Red Blue

[Ti(H2O)6]3+ 498 Blue-green Purple

 In the absence of ligand, crystal-field splitting does not occur; hence, the substance is
colourless. For example, the removal of water from [Ti(H 2O)6]Cl3 on heating renders it
colourless. However, the complex [Ti(H2O)6]3+ is violet in colour.
Limitations of Crystal-Field Theory
 Anionic ligands are assumed to exert the greatest splitting effect. But the anionic ligands are
found at the lower end of the spectrochemical series.
 Crystal-field theory does not take into account the covalent character of bonding between
ligand and the central metal atom.

Bonding in Metal Carbonyls, Stability of Coordination

Compounds & Applications of Coordination Compounds

Bonding in Metal Carbonyls

 Most of the transition metals form homoleptic carbonyls (compounds containing carbonyl
ligands only).
 Structures of some representative homoleptic metal carbonyls are given below.
  The metal−carbon bonds in metal carbonyls have both σ and π characters.
 A σ bond is formed when the carbonyl carbon donates a lone pair of electrons to the vacant
orbital of the metal.
 A π bond is formed by the donation of a pair of electrons from the filled metal d- orbital to the
vacant anti-bonding π* orbital (also known as back bonding of the carbonyl group).
 The σ bond strengthens the π bond, and vice-versa.
 Thus, a synergic effect is created due to this metal-to-ligand bonding. This synergic effect
strengthens the bond between CO and the metal.

Stability of Coordination Compounds

 The stability of a complex in a solution refers to the degree of association between the two
species involved in the state of equilibrium.
 Stability can be expressed quantitatively in terms of stability constant or formation constant.

 For this reaction, the greater the value of the stability constant, the greater is the proportion
of ML4 in the solution.
 Free metal ions are usually surrounded by solvent molecules in solution, which will compete
with the ligands molecules (L) and be successively replaced by them as follows:
 Where, K1, K2, …= Stepwise stability constants

 Alternatively,
Where, β1, β2, …. = Overall stability constant
The stepwise and overall stability constants are therefore related as follows:

or more generally,
 The reciprocal of the formation constant is called instability constant or dissociation
constant.
Applications of Coordination Compounds
 In many qualitative and quantitative chemical analyses: Colour reactions are given by metal
ions with a number of ligands (especially chelating ligands), which help in detection and
estimation.
 Hardness of water can be estimated by simple titration with Na 2EDTA, which forms stable
complexes with Ca2+ and Mg2+ ions.
 Some important extraction processes of metals such as gold and silver make use of complex
formation.
 Coordination compounds are used as catalysts. For example, Wilkinson catalyst, [(Ph 3P)3RhCl],
is used for the hydrogenation of alkenes.
 Chelate therapy is used in medicinal chemistry. For example, EDTA is used in the treatment of
lead poisoning. Some coordination compounds such as cis-platin and related compounds
inhibit the growth of tumours.
 Coordination compounds are of great importance in biological systems. For example,
chlorophyll is a coordination compound of magnesium, haemoglobin is a coordination
compound of iron and vitamin B12 is a coordination compound of cobalt.

MAZHAR SIR
(M.Sc. ORGANIC CHEMISTRY)
CONTACT NO. 7878114456