CHAPTER -5

COORDINATION COMPOUNDS - NOTES

Molecular or Addition compounds
When a solution containing two or more simple stable compounds in molecular
proportions is allowed to evaporate, it produces crystals of new substances known
as molecular or addition compounds.
Types of Molecular compounds
1. Double Salt
A double salt is a substance formed by combining two different salts that
crystallize as a single substance but ionize as two distinct salts when dissolved
in water. These salts lose their identity in solution, which means that when
dissolved in water, they test positive for all of the ions present in the salt.
eg. Mohr's salt, FeSO4(NH4)2SO4. 6H2O.

2. Coordination compounds

Coordination compounds are those addition molecular compounds which retain

their identity in solid state as well as in dissolved state. In these compounds. the
central metal atom or ion is linked by ions or molecules with coordinate bonds.
e.g.,Potassiumferrocyanide, K4[Fe(CN)6].
 Terms Related to Coordination Compounds
1. Complex ion or Coordination Entity:
It is an electrically charged species in which central metal atom or ion is
surrounded by number of ions or neutral molecules.
(i) Cationic complex entity It is the complex ion which carries positive
charge. e.g., [Pt(NH3)4] 2+
(ii) (ii) Anionic complex entity It is the complex ion which carries negative
charge. e.g., [Fe(CN)6] 4-
2. Central Atom or Ion
The atom or ion to which a fixed number of ions or groups are bound is called
central atom or ion. It is also referred as Lewis acid. e.g., in (NiCI2(H2O)4].
Ni is central metal atom. It is generally transition element or inner-transition
element.
3. Ligands
Ligands are electron donating species (ions or molecules) bound to the Central
atom in the coordination entity. These may be charged or neutral. LIgands are of
the following types :
(i) Unidentate: It is a ligand, which has one donor site, i.e., the ligand bound to
a metal ion through a single donor site. e.g., H2O, NH3, etc.

(ii) Didentate: It is the ligand which have two donor sites.

(iii) Polydentate: It is the ligand, which have several donor sites. e.g., [EDTA] 4-
is hexadentate ligand.
(vi) Ambidentate ligands

These are the monodentate ligands which can ligate through two different
- -
sites, e.g., NO2 , SCN , etc.
(v) Chelating ligands:
Di or polydentate ligands cause cyclisation around the metal atom which are
known as chelate , Such ligands uses two or more donor atoms to bind a single
metal ion and are known as chelating ligands. More the number of chelate rings,
more is the stability of complex. The stabilisation of coordination compounds due
to chelation is known as chelate effect.
4. Coordination Number
It is defined as the number of coordinate bonds formed by central metal atom,
with the ligands.
e.g., in [PtCI6] 2- , Pt has coordination number 6.
In case of monodentate ligands, Coordination number = number of ligands
In polydentate ligands. Coordination number = number of ligands denticity
5. Coordination Sphere:
The central ion and the ligands attached to it are enclosed in square bracket
which is known as coordination sphere. The ionisable group written outside the
bracket is known as counter ions.
6. Coordination Polyhedron The spatial arrangement of the ligands which are
directly attached to the central atom or ion, is called coordination polyhedron
around the central atom or ion.
7. Oxidation Number of Central Atom The charge of the complex if all the
ligands are removed along with the electron pairs that are shared with the central
atom, is called oxidation number of central atom.
e.g., [CU(CN4)3- , oxidation number of copper is +1, and represented as Cu(I).

Types of Complexes
1. Homoleptic complexes
Complexes in which the metal atom or ion is linked to only one kind of donor
atoms, are called homoleptic complexes
e.g., [Co(NH3)6] 3+
 2. Heteroleptic complexes
Complexes in which the metal atom or ion is linked to more than one kind of
donor atoms are called heteroleptic complexes e.g., [Co(NH3)4CI2] +
IUPAC Naming of Complex Compounds
Naming is based on set of rules given by IUPAC.
1. Name of the compound is written in two parts (i) name of cation, and (ii) name of
anion.
2. The cation is named first in both positively and negatively charged coordination
complexes.
3. The dissimilar ligands are named in alphabetical order before the name of central
metal atom or ion.
4. For more then one similar ligands. the prefixes di, tri, tetra, etc are added before its
name. If the di, tri, etc already appear in the complex then bis, tris, tetrakis are used.
5. If the complex part is anion, the name of the central metal ends with suffix ‘ate’.
6. Names of the anionic ligands end in ‘0’, names of positive ligands end with ‘ium’
and names of neutral ligands remains as such. But exception are there as we use aqua
for H2O, ammine for NH3, carbonyl for CO and nitrosyl for NO.
7. Oxidation state for the metal in cation, anion or neutral coordination compounds is
indicated by Roman numeral in parentheses.
8. The name of the complex part is written as one word.
9. If the complex ion is a cation, the metal is named same as the element.
10. The neutral complex molecule is named similar to that of the complex cation.
Some examples are
(i) [Cr(NH3)3(H2O)3]Cl3
triamminetrichlorochromium (III) chloride
(ii) [Co(H2CH2CH2H2)3]2(SO4)3
tris (ethane-l,2-diamine) cobalt (III) sulphate
(iii) [Ag(NH3)2] [Ag(CN)2]
diamminesilver (I) dicyanoargentate(I)
(iv) K4 [Fe(CN)6]
potassium hexacyanoferrate (II)

Isomerism in Coordination Compounds

Coordination compounds exhibit the following types of isomerism:

1.Structural Isomerism
In this isomerism isomers have different bonding pattern. Different types of
structural isomers are
(i) Linkage isomerism
This type of isomerism is shown by the coordination compounds having
ambidentate ligands. e.g., [Co(NH3)5(NO2)]Cl2 and [Co(NH3)5(ONO)]Cl2 or
pentaammine nitrito- N Cobalt (III) chloride and pentaammine nitrito-O’Cobalt
(III) chloride.
( ii) Coordination isomerism
This type of isomerism arises from the interchange of ligands between cationic and
anionic complexes of different metal ions present in a complex, e.g., [Cr(NH3)6)
[CO(CN)6]and [CO(NH3)6] [Cr(CN)6]
(iii) Ionisation isomerism
This isomerism arise due to exchange of ionisable anion with anionic ligand. e.g.
 iv) Solvate isomerism (Hydrate isomerism)
In this isomerism, water is taken as solvent. It has different number of water
molecules in the coordination sphere and outside it.
e.g.. [Co(H2O)6]CI3, [Co(H2O)4C12]Cl·2H2O, [Co(H2O)3Cl3]. 3H2O

2. Stereoisomerism
Stereoisomers have the same chemical formula and chemical bonds but they have
different spatial arrangement.
These are of two types :
a) Geometrical isomerism
Geometrical isomers are of two types i.e., cis and trans isomers. This isomerism
is common in complexes with coordination number 4 and 6.
Geometrical isomerism in complexes with coordination number 4
(i) Tetrahedral complexes do not show geometrical isomerism.
(ii) Square planar complexes of formula [MX2L2] (X and L are unidentate)
show geometrical isomerism. The two X ligands may be arranged adjacent
to each other in a cis isomer, or opposite to each other in a trans isomer,
e.g.,

(iii) Square planar complex of the type [MABXL] (where A, B, X, L, are unidentate
ligands) shows three isomers, two cis and one trans.
e.g., [Pt(NH3) (Br)(Cl)(Py)].
Geometrical isomerism in complexes with coordination number 6
Octahedral complexes of formula [MX2L4], in which the two X ligands may be
oriented cis or trans to each other, e.g., [Co(NH3)4Cl2) + .

Octahedral complexes of formula [MX2A2], where X are unidentate ligands and

 A are bidentate ligand. form cis and trans isomers,
e.g., [CoC12(en)2]
In octahedral complexes of formula [MA3X3], if three donor atoms of the same
ligands occupy adjacent positions at the corners of an octahedral face. it is known as
facial (fac) isomer, when the positions are around the meridian of the octahedron, it
is known as meridional (mer) isomer. e.g., [Co(NH3)3(NO2)3]

b) Optical isomerism
These are the complexes which have chiral structures. It arises when mirror
images cannot be superimposed on one another. These mirror images are
called enantiomers. The two forms are called dextro (d) and laevo (l) forms.
Tetrahedral complexes with formula [M(AB) 2] show optical isomers and
octahedral complexes (cis form) exhibit optical isomerism.

Bonding in Coordination Compounds

Werner’s Theory
Metals exhibit two types of valencies in the formation of complexes. These
are primary valencies and secondary valencies.
1. Primary valencies correspond to oxidation number (ON) of the metal
and are satisfied by anions. These are ionisable and non-directional.
2. Secondary valencies correspond to coordination number (CN) of the
metal atom and are satisfied by ligands. These are non-ionisable and
directional. Hence, geometry is decided by these valencies.
 Valence Bond Theory (VBT)
The following assumptions are made by VBT:

(i) The central metal ion has a number of empty orbitals that can accept
electrons donated by the ligands. The coordination number of the
metal ion for the specific complex is equal to the number of empty
d-orbitals.
(ii) Strong bonds are formed when the metal orbitals and ligand orbitals
overlap. The greater the extent of overlapping, the more stable the
complex. Different orbitals (s, p, or d) hybridize to form a set of
equivalent hybridized orbitals that participate in ligand bonding.

(iii) Each ligand contributes two electrons to the central metal ion/atom.

(iv) The inner orbitals contain non-bonding metal electrons that do not
participate in chemical bonding.

(v) A complex is paramagnetic if it contains unpaired electrons. The

complex is diamagnetic if it does not contain an unpaired electron.

Paramagnetism can be calculated by the expression,

µ= , where µ = magnetic moment (which is

calculated in Bohr magneton
i.e. B.M.),

n = number of unpaired electrons.

(vi) Under the influence of a strong ligand (CN, CO), electrons can be
forced to pair up, thereby violating Hund's rule of multiplicity.

FORMATION OF COMPLEXES: REFER TEXT BOOK

NOTE:
Inner d-orbitals (3d orbital) have been used for bonding in d2 sp3 hybridisation;
such complexes are known as inner orbital complexes or low spin complexes. The
outer d-orbitals (4d orbital) have been used for bonding in sp3 d 2 hybridisation;
such complexes are known as outer orbital complexes or high spin complexes.
Limitations of VBT
(i) It involves a number of assumptions.
(ii) (ii) It does not give quantitative interpretation of magnetic data.
(iii) (iii) It does not explain the colour exhibited by coordination
compounds.
(iv) (iv) It does not give a quantitative interpretation of the thermodynamic
or kinetic stabilities of coordination compounds.
(v) (v) It does not make exact predictions regarding the tetrahedral and
square planar structures of 4-coordinate complexes.
(vi) (vi) It does not distinguish between weak and strong ligands.
CRYSTAL FIELD THEORY
The crystal field theory was proposed by Hans Bethe and VanVleck. This theory gives
satisfactory explanation for the bonding and the properties of complexes than the
valence bond theory.
Assumptions of Crystal field theory:
The interaction between the metal ion and the ligand is purely electrostatic.
Negative ligands are treated as point charges and neutral ligands are treated as dipoles.
The five d-orbitals in an isolated gaseous metal atom (or) ion are degenerate.
The repulsions between the electrons in the metal ion and the ligands increases the
energy of the d-orbitals and lifts the degeneracy in d-orbitals. This results in the d-
orbitals getting split.
Crystal field splitting in octahedral complexes:

In octahedral complexes, the metal ion is at the centre of the octahedron, and the six
ligands lie at the six corners of the octahedron along the three axes X, Y and Z. The
dx2- y2 and d z square orbitals are together known as the eg set of orbitals.

The dxy, dxz and dyz orbitals are collectively known as the t2g set of orbitals.

Under the influence of the ligands, the degeneracy of the five d orbitals of the metal
ion is lost and they are split into two groups of orbitals of different energies. This
effect is known as crystal field splitting.

The pattern of splitting of the d orbitals depends on the number of ligands and their
arrangement around the central metal atom or ion.
The magnitude of crystal field splitting depends upon the field strength of the ligand
and the charge on the metal ion.
Ligands that cause only a small degree of crystal filed splitting are termed weak field
ligands, while ligands that cause a large splitting are called strong field ligands.
Complexes formed with weak field ligands would be high-spin complexes.
Complexes formed with strong field ligands would be low-spin complexes.

Common ligands can be arranged in ascending order of field strength is,

I- < Br - < SCN - < Cl - < S2- < F- < OH - < C2O42- < H2O < NCS - edta4 - NH3 < en <
CN- < CO
The order remains practically constant for different metals and this series is called the
spectro-chemical series. It is an experimentally determined series based on the
absorption of light by complexes with different ligands.
Crystal field splitting in Octahedral complexes:

Crystal field splitting in tetrahedral complexes:

In a tetrahedral field, the crystal field splitting for the same metal, the same ligands
and metal ligands is
Δt = 4/9 Δ0
Colour in Coordination Compounds
The crystal field theory attributes the colour of the coordination compounds to d-d
transition of the electron, i.e., electron gets excited from t2g level to higher eg level.
In the absence of ligands, crystal field splitting does not occur and hence the
substance is colourless.
Limitations of CFT
1. It does not consider the formation of covalent bonding in complexes.
2. It is also unable to account satisfactorily for the relative strengths of ligands e.g., it
does not explain why H2O is stronger ligand than OH- .
3. It gives no account of the partly covalent nature of metal-metal bonds.
METAL CARBONYLS
Metal carbonyls are compounds formed by combining metal and carbon monoxide.
These compounds have sigma and pi bonding. Metal atoms in these compounds have
no oxidation state. Carbonyls can be monomeric, bridged, or polynuclear in nature.

BONDING IN METAL CARBONYLS

In Metal Carbonyls, the metal and carbon bond (M-C) possess both s and p character.

The M-C sigma bond is formed by donating the lone pair of electrons on the carbonyl
carbon into a vacant orbital of the metal and the M-C pi bond is formed by donating
the lone pair of electrons from a filled d orbital of metal to the vacant antibonding pi*
orbital of the carbon monoxide. This back bonding property which stablises the
metal ligand interaction is termed as the Synergic Bonding.