Co-Ordination Complexes

Prof. Amala Shrestha

Introduction
• Additional or Molecular Compounds
• When two normal salts solution are mixed in equimolar quantities and
the solution is evaporated to crystallization point, we get the crystals of
new compound called Additional or Molecular Compounds
• The formation of some Additional Compounds has been shown below
Simple Compounds Additional Compounds
KCl MgCl2 6H2O K+Cl- Mg++ 2Cl-
KCl + MgCl2 + 6H2O
Carnalite
K2SO4 + Al2(SO4)3+ 24H2O K2SO4 Al2(SO4)3 24H2O 2K+SO4- - 2Al+3 3SO4- -
Potash Alum
(NH4)2SO4 + FeSO4 + 6H2O FeSO4 (NH4)2SO4 6H2O Fe+2SO4 -2 2NH4+ SO4-2
Mohr’s Salt
CuSO4 + 4NH3 CuSO44NH3 or [Cu(NH3)4]SO4 [Cu(NH3)4]2+ SO4 -2
Tetramminc Copper Sulphate
Fe(CN)2 + 4KCN Fe(CN)2 4KCN or K4[Fe(CN)6] 4K+ [Fe(CN)6]4-
Potassium Ferrocyanide
Introduction
• Types of Additional Compounds
1. Double Salt or Lattice Compound
2. Complex Salt or Co-Ordination Compound

3. Double Salt or Lattice Compound

• These are the additional compounds which are stable in the solid state.
• When they dissolve in water, they ionize to give constituent ions, hence
they give the test of all the ions present in the constituent component salt.
• For example, when Carnalite KClMgCl26H2O dissolves in water it ionizes to
give K+ Mg+2 and Cl- ions hence they give the test of K+ Mg+2 and Cl- ions i.e.
double salt does not loose the properties of constituent ions
Introduction
2. Complex Salt or Co-Ordination Compound
• These are the additional compounds which does not give all their
constituents ions when dissolved in water.
• Hence they do not give the test of all the ions present in the
constituent component salts.
• For example, when Potassium Ferrocyanide K4[Fe(CN)6] dissolves in
water it ionizes to give 4K+ and [Fe(CN)6]4- ions. Hence they give the
test of K+ and Fe[CN)6]4- ions. It does not give the test of Fe+2 and CN-
ions i.e. complex salt looses the properties of constituent component
salts
Differences between Double and Complex Salts
Double Salt Complex Salt
i. They contain two salts which may or may not
i. They contain two salts in equimolar ratio be in equimolar ratio
ii. They exist in solid state ii. They exist in solid as well as in aqueous form
iii. They form simple and compound ions in iii. They form complex ion in aqueous solution
aqueous solution e.g. K+, Al+3, SO4-2 e.g. [Fe(CN)6]4-

iv. They do not have co-ordinate bonds between

metal and the attached species iv. They have co-ordinate bonds

v. They do not lose their identity in aqueous

v. They lose their identity in aqueous solution
solution

vi. In double salts, metal ions show their normal vi. In complex salts, metal ions show primary
valencies (Oxidation state of the metal) valencies (Oxidation state) and secondary
valencies (number of ligands)
Definition of Complex Compound
• In 1893, Alfred Werner gave the definition of Complex Compound
• According to him, “Certain metal atoms / ions generally the transition
metals have tendency to attach themselves definite number of atoms,
ions or molecules forming closely associated charged ions known as
Complex ions (Cations or Anions)”.
• The salt which gives complex ions in solution is known as Complex
Compound.
Terms used in Complex Compound
• Different terms are used in complex compound. These are
i. Complex ion
ii. Ligands
iii. Co-ordination Number (CN) or Ligancy
iv. Central Metal atom / ion
v. Co-ordination Sphere
vi. Outer Sphere
Terms used in Complex Compound
i. Complex ion
Complex ion is positively or negatively charged species which contains a central
metal atom and suitable number of ligands surrounding the central metal atom.
The central metal atom may be in zero, positive (oxidation) state.
e.g.
[CO+3(NH3)6]3+, [Fe+2(CN)6]4-, [Ni0(CO)4]0
ii. Ligands
The atoms, ions or neutral molecules attached to the metal atom in complex
compounds are called ligands or co-ordinating groups. For example in the complex
ion [Fe+2(CN)6]4-, the six CN- ions are attached with central Fe+2 ion. The ligand must
have at least one lone pair of electron which donates to the metal atom / ion. The
ligand acts as Lewis base and the central metal atom / ion acts as a Lewis acid.
M + L M L
Central Metal Ligand
atom / ion
Terms used in Complex Compound
 Type of Ligands
On the basis of donor atoms, the ligands are classified into following types
a. Monodentate Ligands or Unidentate Ligands
 The ligands which have only one donor atom and hence can co-ordinate to the central
metal ion at one site forming only one co-ordinate bond are called Monodentate Ligands
or Unidental Ligands.
 These ligands may be neutral molecules, negatively charged ions or positively charged
ions.
 e.g. are H2O, NH3, CO, NO, F-, Cl-, Br-, CN-, OH-, NO+, NH2NH3+
b. Bidentate Ligands
 The ligands having two donor atoms and hence can co-ordinate to the central metal ion
at two sites forming two co-ordinate bond are called Bidentate Ligands (dentate means
toothed).
 e.g. O = C O- Oxalate NH2NH2 ethylendiamine
ion
O = C O-
Terms used in Complex Compound
 Type of Ligands
c. Polydentate Ligands or Multidentate Ligands
 The ligands which having two, three, four, five or six donor atoms and hence can donates
two, three, four, five or six lone pairs of electrons forming two, three, four, five or six co-
ordinate bonds are said to be Polydentate ligands or Multidentate Ligands.
 The polydentate ligands always form a ring structure compounds called Chelates and the
ligands are known as Chelating ligands. e.g. EDTA (EthyleneDiamineTetracetic Acid)

COO- Oxalate
ion
COO-
Terms used in Complex Compound
iii. Co-ordination Number (CN) or Ligancy
The no. of co-ordinate bond around the metal atom/ ion is the co-ordination
no. of the metal atom/ ion
iv. Central Metal atom / ion
When the ligands are attached with the metal atom / ion, then the metal atom / ion
is said to be central metal atom / ion
v. Co-ordination Sphere or Nonionizable Sphere
While writing the structural formula of the complex compound, central metal atom /
ion and the ligands are always written in a bracket [ ], this forms the co-ordination
sphere. The species inside the bracket do not ionize in solution, hence do not give a
test with suitable reagent. So this is also known as nonionizable sphere.
vi. Outer Sphere
The species which are written outside the bracket form the outer sphere which
ionizes in solution, hence gives a test with suitable reagent.
 Terms used in Complex Compound

Ligand
Central metal ion Outer Sphere

[Co(NH3)6] Cl3
Co-ordination Sphere Co-ordination Number

[Co(NH3)6]3+ 3Cl-
Complex Ion
Werner’s Co-ordination Theory
• In 1893, Alfred Werner put forward a theory known as Werner’s theory
to explain the structure and properties of Co (III) ammines.
• These ammines are CoCl3, 6NH3, CoCl35NH3, CoCl34NH3 and CoCl33NH3.
• This theory is based on the following postulates or assumptions (next
slide).
Postulates of Werner’s Theory
1. Metal possesses two types of valencies
i. Primary or Principal or Ionizable Valency
ii. Secondary or Auxiliary or Nonionizable Valency
2. Characteristics of Secondary Valency
i. The atoms, ions or molecules attached with the metal atom / ion are
known as ligands. The number of ligands attached with the metal atom
/ ion is the secondary valency of the metal atom. In modern
terminology the secondary valency is known as co-ordination number
(CN) of the metal atom / ion.
Postulates of Werner’s Theory
2. Characteristics of Secondary Valency
ii. Secondary valency of the metal is satisfied either by negative ions or by
neutral molecules alone or by both anions and neutral molecules. For
example
a. In K4[Fe(CN)6], the secondary valency of Fe atom is six and is satisfied by
six CN- ions (anions)
b. In [Co(NH3)6]Cl3, the secondary valency of Co atom is six and is satisfied by
six NH3 molecules (neutral molecules)
c. In [Co(NH3)4Cl2]Cl, the secondary valency of Co is six and is satisfied by
four NH3 molecules (neutral molecules) and two Cl - ions (anions)
Postulates of Werner’s Theory
2. Characteristics of Secondary Valency
iii. Every metal atom / ion has fixed co-ordination number or secondary valency
e.g. Ni+2CN = 4, Zn+2CN = 4, Fe+2 and Fe+3 CN = 6
iv. While writing the formula of the complex compound, the species satisfying
the secondary valency and the metal are written inside the bracket or co-
ordination sphere [ ]. The species inside the bracket do not ionize in solution,
hence do not give a test with suitable reagent.
v. The secondary valency have directional character, since the species satisfying
the secondary valency (ligands) are directed towards the fixed position in the
space giving definite geometrical shape. For example, if the metal atom / ion
has six secondary valency, the six ligands are situated at the six corners of
the regular octahedron and the metal atom lie at the center of the
octahedron
Postulates of Werner’s Theory
2. Characteristics of Secondary Valency
vi. The species satisfying the secondary valency gives the geometry of the
complex compound
vii. The species satisfying the secondary valency never occurs in free state i.e.
they are not ionizable, hence do not give test with suitable reagent
viii. In writing the structure of the complex compound the attachment of the
species satisfying the secondary valency with the metal atom is shown by
a solid line ( )
3. Characteristics of Primary Valency
i. The primary valency of a metal atom in a given complex compound is the
oxidation number of the metal atom.
ii. The primary valency of a metal in a complex compound is always satisfied
by anions (negative ions)
Postulates of Werner’s Theory
3. Characteristics of Primary Valency
iii. The species satisfying the primary valency only is written outside the
bracket and ionizes in solution, hence gives a test with suitable reagent.
While the anions satisfying both valencies (Primary and Secondary) are
written inside the bracket or co-ordination sphere. Thus the species
satisfying primary valency may be present inside and outside the co-
ordination sphere.
iv. The species satisfying the primary valency do not give the geometry to
the complex compound
Postulates of Werner’s Theory
3. Characteristics of Primary Valency
v. The species satisfying the primary valency may or may not occur in free
form. e.g.
[Co(NH3)6]Cl3 [Co(NH3)6]3+ + 3Cl-
The three Cl- satisfy only the primary valency
In [Co(NH3)4Cl2]Cl [Co(NH3)4Cl2]+ + Cl-
Although the primary valency of Co is satisfied by three Cl- Ions only one
Cl is obtained in free state. From above discussion we conclude that all
the anions placed outside the co-ordination sphere can be obtained in
free state and hence can be precipitated.
Postulates of Werner’s Theory
3. Characteristics of Primary Valency
vi. The attachment of the species satisfying the primary valency to the
metal is shown by broken line ( )
vii. The attachment between the metal and the species which satisfy both
the valencies is shown by both lines solid as well as broken line ( )
Explain the structure of Co(III) ammines on the
basis of Werner’s theory
• With the help of Werner’s theory, the structure of Co(III) ammines viz
CoCl3.6NH3, CoCl3.5NH3, CoCl3.4NH3 and CoCl3.3NH3 can be well
explained.
• In all these ammines, the primary valency of Cobalt is equal to +3 while
the secondary valency is equal to 6.
• The primary valency of +3 is satisfied by three Cl- ions and hence these
ions are attached with Co+3 ion by dotted line ( )
• Secondary valency of six is satisfied either by six NH3 molecules alone
or by NH3 molecules and Cl- ion and the attachment with Co +3 is shown
by solid line ( ).
Explain the structure of Co(III) ammines on the
basis of Werner’s theory
1. Structure of CoCl3.6NH3:
• When this ammines is treated with AgNO3 solution, three moles of AgCl are
precipitated out.
CoCl3.6NH3 [Co6NH3]3+ + 3Cl-
3AgNO3+ 3Cl- 3AgCl + 3NO3-
3 moles
• This precipitation of all the three Cl- ions indicates that these ions are obtained in
free form or ionize and are written outside the bracket and it is only six NH3
molecules along with Co+3 atom inside the bracket.
• Thus the structure of CoCl3.6NH3 can be written as [Co6NH3]+3Cl3 or [Co(NH3)6]3+
Cl3.
• This formula shows that the secondary valency of Co atom is equal to six is
satisfied by six NH3 molecules and is written inside the bracket.
Explain the structure of Co(III) ammines on the
basis of Werner’s theory
1. Structure of CoCl3.6NH3:
• Hence the attachment of NH3 molecules with Co atom is shown by solid
line ( ).
• The structure is
Cl- NH3 NH3
NH3

Co +3 Cl-
NH3

Cl- NH3 NH3

Explain the structure of Co(III) ammines on the
basis of Werner’s theory
2. Structure of CoCl3.5NH3:
• Primary valency of Co atom is equal to +3 and is satisfied by three Cl- ions. Attachment of
these ions with Co+3 is shown by broken line ( )
• The treatment of this ammine with AgNO3 solution precipitates only two Cl- ions as AgCl
CoCl3.5NH3 [CoCl5NH3]2+ + 2Cl-
2AgNO3 + 2Cl- 2AgCl + 2NO3-
2 moles
• This precipitation of only two Cl- ions indicates that two Cl- ions ionize and are written
outside the bracket and the remaining one Cl- ion and five NH3 molecules are present
inside the co-ordination sphere.
• From this observation, the structure CoCl3.5NH3 can be written as [Co5NH3 Cl]Cl2 or
[Co(NH3)5 Cl] Cl2.
Explain the structure of Co(III) ammines on the
basis of Werner’s theory
2. Structure of CoCl3.5NH3:
• On basis of Werner’s theory, the structure of CoCl3.5NH3 can be shown as

Cl- NH3
NH3

Co +3 Cl-
Cl-

NH3 NH3 NH3

Explain the structure of Co(III) ammines on the
basis of Werner’s theory
3. Structure of CoCl3.4NH3:
• The primary valency of Co atom is equal to +3 and is satisfied by three Cl-
ions and hence the attachment of these ions with Co+3 is shown by the
broken line ( ).
• The treatment of this ammine with AgNO3 solution precipitates only one
Cl- ion as AgCl
CoCl3.4NH3 [CoCl24NH3]+ + Cl-
AgNO3 + Cl- AgCl + NO3-
1 moles
• This precipitation of one Cl- ion indicates that one Cl- ion ionize and is
written outside the bracket and the remaining two Cl- ions and four NH3
molecules are written inside the bracket.
Explain the structure of Co(III) ammines on the
basis of Werner’s theory
3. Structure of CoCl3.4NH3:
• Thus, the structure of CoCl3.4NH3 can be represented as [CoCl24NH3] Cl or
[Co(NH3)4 Cl2] Cl.
• The secondary valency of Co atom is equal to six which is satisfied by four
NH3 molecules and two Cl- ions.
• Hence the attachment of these six species with Co atom has been shown
by solid line ( ).
Explain the structure of Co(III) ammines on the
basis of Werner’s theory
3. Structure of CoCl3.4NH3:
• Thus on the basis of Werner’s theory, the structure of CoCl3.4NH3 can be
shown as

Cl- NH3
NH3

Co +3 Cl-

NH3 NH3
Cl-
Explain the structure of Co(III) ammines on the
basis of Werner’s theory
4. Structure of CoCl3.3NH3:
• The primary valency of Co atom is equal to +3 and is satisfied by three Cl-
ions.
• Hence the attachment of these ions with Co atom is shown by the broken
line ( ).
• When this ammine is treated with AgNO3 solution, no precipitate is
obtained.
• This indicates that no chloride ion ionizes and no Cl- ion is outside the
bracket.
• All the three Cl- ions and three NH3 molecules along with Co atom are
present inside the bracket.
Explain the structure of Co(III) ammines on the
basis of Werner’s theory
4. Structure of CoCl3.3NH3:
• Thus, the structure of this ammine can be written as [CoCl3.3NH3] or
[Co(NH3)3 Cl3].
• This shows that the secondary valency of Co atom is equal to six is
satisfied by three Cl- ions and three NH3 molecules.
• Thus the attachment of these species with Co atom has been shown by
solid line ( ) in which three Cl- ion is shown by both lines solid and
broken lines ( )

CoCl3.3NH3 X
no ppt with AgNO3
Explain the structure of Co(III) ammines on the
basis of Werner’s theory
4. Structure of CoCl3.3NH3:

Cl- NH3
NH3

Co+3

Cl- Cl-
NH3
Sidgwick’s Electronic Interpretation of Co-
ordination
• Sometimes called as Sidgwick’s Concept of Co-ordinate Bond or
Sidgwick’s Model
• Until the advent of electronic theory of valency, Werner’s theory was
regarded as satisfactory to explain the structure of complex compound.
• But with the advent of electronic theory of valency, it was necessary to
make some modifications in Werner’s theory.
• Sidgwick in 1927 explained the bonding in complex compound on the
basis of electronic theory of valency.
• He accepted Lewis concept of two electrons covalent bonds between
two atoms in molecule and introduced the new concept of Co-ordinate
bond
Sidgwick’s Electronic Interpretation of Co-
ordination
• He says that the ligands are atoms, ions or molecules having an atom
which contains at least one lone pair of electron.
• He further says that when the ligands are attached with the central
metal atom / ion, the ligand donates a pair of electron to the central
metal atom / ion.
• The atom which donates the electron pair is known as donor.
• The atom which accepts the electron pair is known as an accepter.
• The pair of electron donated are lone pair and the donation of electron
pair is shown by an arrow pointing from donor to the accepter and is
known as co-ordinate bond
Sidgwick’s Electronic Interpretation of Co-
ordination
M L
accepter donor
• The ligand L donates as pair of electron to metal atom M.
• Thus on this basis of Sidgwick’s concept, the structure of the complex
ion [Co(NH3)6]3+ can be shown as NH3 NH3
3+

NH3

Co+3
Formation of Six Co-ordinate Bonds
Between Six NH3 molecule and Co+3 ion NH3 NH3
NH3
Sidgwick’s Electronic Interpretation of Co-
ordination
• Evidently, in the formation of bonds between the six ligands (NH 3
molecule) and the central Co+3 ion, the N atom of each NH3 molecule
donates an electron pair to Co+3 ion.
• Thus, in all twelve electrons i.e. six electron pairs are donated by six
NH3 ligands to Co+3 ion.
• The donation of an electron pair by NH3 molecule has been shown by
an arrow pointing from donor to accepter ie NH3 to Co+3
• This is the structure of [Co(NH3)6]3+ ion and is known as Sidgwick’s
model.
Limitation of Sidgwick’s Concept
• The donation of one electron pair by ligand to the central metal ion to
form L M co-ordinate bond in complex accumulates negative
charge on the central metal atom /ion in which is most unlikely
• This makes the complex compound unstable.
• This defect is easily removed by Pauling on the basis of electro-
neutrality theory
Sidgwick’s Effective Atomic Number (EAN) rule
• Sidgwick further says that after the ligands have donated a certain
number of electron to the central metal ion through L M bonding,
the total number of electron on the central atom, including those
gained from the ligands is called effective atomic number (EAN) of the
central metal atom / ion which is always equal to the atomic number of
the nearest inert gas.
• Hence this rule is also known as noble gas rule.
Calculation of EAN of the Central Metal Atom /
Ion in the Complex ion
• The EAN of the central metal atom / ion in given complex ion is given
by
EAN = (z – x) + n x y
where z = atomic no. of the central metal atom
x = oxidation no. of central metal atom
n = no. of ligands
y = no. of electron donated by each ligands
EAN of Co+3 = (z – x) + n x y = (27 – 3) + 6 x 2 = 24 + 12
= 36
= Atomic no. of Kr
Application of EAN rule
• EAN rule is used to predict the stability and the magnetic properties of the
complexes
• It has been observed that the complex ion whose central metal atom obeys EAN rule
are stable and diamagnetic.
• The complex ion whose central metal atom does not obey EAN are generally
unstable and paramagnetic.
• The paramagnetic character is due to the presence of one or more unpaired
electron.
• The no. of unpaired electron is the difference between EAN and atomic number of
nearest inert gas
In [Fe(CN)6]3-
EAN of Fe+3 = (z – x) + n x y = (26 – 3) + 6 x 2 = 23 + 12
= 35 ≠ Atomic no. of Kr = unstable and paramagnetic
No. of unpaired electron = Atomic no. of Kr – EAN = 36 – 35 = 1
Exception to the EAN rule
• The complexes of Fe+3, Ni+2, Co+2 and Ag+ never valid the EAN rule

• Describe a simple test to distinguish between the following pairs of

compounds:
1. [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br
2. [Pt(NH3)4Cl2]Br2 and [Pt(NH3)4Br2]Cl2
Nomenclature of Co-ordination Complexes
• Co-ordination complexes are named according to the rule suggested by
International Union of Pure and Applied Chemistry IUPAC (1976) which is
modified in 2004. According to this rule the complexes name should begin
with small letters
• Theses rules are as follows
1. If the complex compound is ionic i.e. the complex compound is made up of
cation and anion, the cation is named first then the anion
For example,
i. K4[Fe(CN)6] 4K+ + [Fe(CN)6]4-, K+ is named first then the
name of anion
ii. [Co(NH3)6] Cl3 [Co(NH3)6]3+ + 3Cl-, [Co(NH3)6]3+ is named first
then the name of anion
Nomenclature of Co-ordination Complexes
2. If the complex compound is nonionic (neutral), the named complex
compound is written as one word
For example,
[Cr(NH3)3 Cl CN NO2]0 is written as one word
3. In the complex ion or co-ordination sphere, the ligand is named first then
the central metal atom / ion.
4. If there are different ligands, these are named in alphabetical manner.
5. If there are more than one simple ligand of same kind, these are prefixed
by di (for 2), tri (for 3), tetra (for 4), penta (for 5), hexa (for 6) and so on
Nomenclature of Co-ordination Complexes
6. If the ligands are complex one generally the organic neutral ligands which
already have di, tri etc. in their names. These are prefixed by bis (for 2),
tris (for 3), tetrakis (for 4), pentakis (for 5) etc. and the name of the ligand
is enclosed in a bracket
[Cr(en)3] Cl3 en = ethylenediamine
tris (ethylenediamine) chromium (III) chloride
[Pt(Py)4]0 Py = Pyredine
tetrakis (pyredine) platinum (0)
Nomenclature of Co-ordination Complexes
7. Naming of ligands
i. If the name of the negative ligands end in –ide, the ide is changed into o. For
example
Fluoride F- - Fluoro Chloride Cl- - Chloro
Cyanide CN- - Cyano
ii. If the name of the negative ligands end in –ate or -ite, the e is changed into o. For
example
Sulphate SO4-- - Sulphato Sulphite SO3- - Sulphito
Nitrate NO3- - Nitrato Nitrite NO2- - Nitrito
Oxalate C2O4--
iii. For neutral ligand water is changed into aqua and ammonia to ammine, other
neutral ligands have no special endings.
iv. The name of the positive ligands end in -ium
H3O+ - Hydronium NO+ - Nitrosonium
Nomenclature of Co-ordination Complexes
8. The ligands so named is followed by the name of the central metal atom
with oxidation no. in Roman in a bracket.
9. If the complex ion is cation or co-ordination sphere is neutral, the name
of the metal atom is represented by its usual name. For example
[Co(NH3)6] Cl3 hexa-amminecobalt (III) chloride
[Cr(NH3)3 Cl CN NO2] triamminechlorocyanonitritochromium (III)
10.If the complex ion is anion, the name of the central metal atom is made
to end in -ate. For example
K4 [Fe(CN)6] potassium hexacyanoferrate (II)
Write the IUPAC names of the following complex compounds

• Cationic complexes • Anionic complexes • Neutral complexes

1. [Co(NH3)6]Cl3 1. K4[Fe(CN)6] 1. [Cr(C6H6)2]
2. [Co(NH3)5SO4]NO3 2. Na2[ZnCl4] 2. [Co(NO2)3(NH3)3]
3. [Cr(H2O)4(NH3)2]Br2 3. K3[Ag(S2O3)2] 3. [PtCl2(C2H4)NH3]
4. [Fe(H2O)6]SO4 4. K3[Al(C2O4)3] 4. [Pt(Py)4]
5. [Co(NH3)5CO3]Cl 5. [AlF6]3- 5. [CuCl2(CH3NH2)2]
6. [Cr(H2O)5Cl]Cl2 6. (NH4)3[Al(CN)5Cl] 6. [Co(NO2)3(NH3)3]
7. [Pt(NH3)4Cl(NO2]SO4 7. [Pb(OH)4]2- 7. [PtCl4]
8. [Cr(en)3]Br3 8. Na[Ag(CN)2]
9. [Pt(Py)4] [PtCl4]
Valency Bond Theory of Complexes (VBT)
• This theory is mainly due to Pauling.
• It deals with the
i. electronic configuration of the central metal atom
ii. kind of bonding
iii. geometry
iv. magnetic properties of the complexes.
Postulates of VBT
• This theory is based on the following postulates
1. The central metal atom / ion provides a no. of vacant or empty atomic
orbitals s, p, d equal to the co-ordination number (CN) of the central
metal atom / ion for the formation of bonds with the ligands.
2. The vacant orbitals hybridise together to form hybrid orbitals which are
same in number as the atomic orbitals hybridising together. These hybrid
orbitals have same shape ( ) are vacant, equivalent in energy and have
definite geometry.
3. The ligands are atoms or ions or molecules having at least one lone pair
of electron, which  donates to the central metal atom / ion
L M 𝜎
Postulates of VBT
4. In the formation of complexes, the orbitals of the ligand having lone pair
of electron overlaps axially with the vacant hybrid orbitals of the central
metal atom / ion to form Ligand Metal  (sigma) bond.
5. The geometry of the hybrid orbitals gives the geometry of the complex
compound.
6. The strong field ligands such as CN-, NO3-, NO2-, CO, NO, NH3 and organic
ligands have tendency to pair up the unpaired electron in (n – 1)d orbital
i.e. back pairing of electron in (n – 1)d orbitals and weak ligands such as
F-, Cl-, Br-, I- and H2O have no tendency to pair up the unpaired electron in
(n – 1)d orbital i.e. no back pairing in (n – 1)d orbitals.
Postulates of VBT
7. If d orbitals are used in hybridization, which may be (n – 1)d or nd
orbitals. If the complexes are formed by using (n – 1)d orbital in
hybridization such complexes are known as inner orbital complexes. If nd
orbitals are used in hybridization, the complexes formed are known as
outer orbital complexes.
8. If the electronic configuration of complex compound / ion contains no
unpaired electron n = 1 such complexes are diamagnetic. If the
configuration contains one or more unpaired electrons n = 1, 2, 3, ……….
etc such complex compounds / ions are paramagnetic.
Applications of VBT
• VBT is used to predict the geometry and the magnetic properties of the
complex compound / ion. There are different types of complexes.
Among them the important complexes are
1. Tetrahedral Complexes
2. Square Planar Complexes
3. Octahedral Complexes
Applications of VBT
1. Tetrahedral Complexes
• These complexes are formed as a result of SP 3 hybridization in the central
metal atom / ion.
• These are generally formed by weak field ligands.
• Sometimes these are also formed by strong field ligands in which the
central metal atom / ion has (n – 1)d 9 and (n – 1)d10 configuration, which is
unable to make one vacant (n – 1)d orbital.
• E.g. are
• [NiCl4]2-, [MnCl4]2-, [FeCl4]2-, [FeCl4]-, [COF4]2-, [CoF4]-, [Ni(CO)4]0, [Cu(CN)4]2-,
[Cu(CN)4]3-, [Zn(NH3)4]2+
Formation of [NiCl4]2- - tetrachloronickelate (II) ion
• In this complex ion, Ni is the central atom with Oxidation Number (ON) +2 and
Co-ordination Number (CN) is four, so it has either tetrahedral or square
planar geometry
Applications of VBT
1. Tetrahedral Complexes
Formation of [NiCl4]2- - tetrachloronickelate (II) ion
• Use VBT to explain the correct geometry and the magnetic properties
i. Ni (z = 28) [Ar] 3d84s2 3d 8 4s 2
4p0 4d 0

n=2
ii. Ni+2 [Ar] 3d84s0
n=2
Since Cl- ion is a weak field ligand, so no back pairing sp3 hybridization
of electron in 3d orbital so 3d orbital can’t be made
vacant. Hence Ni+2 undergoes sp3 hybridization

iii. Hybridization in Ni+2 n=2

sp3 hybrid orbitals
iv. [NiCl4]2- n=2
Cl- Cl- Cl- Cl- paramagnet
Applications of VBT 2-
Cl-

Ni+2

Cl- Cl-

Cl-
sp3 hybridization in Ni+2 in [NiCl4]2- which has tetra hedral geometry
Applications of VBT
1. Tetrahedral Complexes
Formation of [NiCl4]2- - tetrachloronickelate (II) ion
Conclusion
• Since this complexion is formed by sp3 hybridization, hence it has tetrahedral
geometry.
• The electronic configuration of this complex ion contains two unpaired electron n
= 2, hence it is paramagnetic.
Applications of VBT
1. Tetrahedral Complexes
Formation of [NiCO)4]0 - tetracarbonylnickel (0)
• In this complex compound Ni is the central atom with zero oxidation state and
four co-ordination number.
• Hence it has either tetrahederal or square planar geometry.
• Use VBT to explain the correct geometry and the magnetic properties
3d8 4s2 4p0 4d0
i. Ni (z = 28) - [Ar] 3d84s2 n=2

Since CO is a strong field ligand, when four CO ligands come close to Ni 0, the
energy released is used to force to excite the paired 4s electrons to 3d orbitals
and 3d orbitals are all paired and 4s orbital is made vacant
Applications of VBT
1. Tetrahedral Complexes
Formation of [NiCO)4]0 - tetracarbonylnickel (0)
ii. Ni0 in [Ni(CO)4] [Ar] 3d104s0
n=0
So Ni undergoes sp3 hybridization sp3 hybridization

iii. Hybridization in Ni0 n=0

sp3 hybrid orbitals
iv. [NiCO4]0
n=0
CO CO CO CO
Applications of VBT
1. Tetrahedral Complexes
Formation of [NiCO)4]0 - tetracarbonylnickel (0)
Conclusion
• Since this complex compound is formed by sp3 hybridization, hence it has
tetrahedral geometry.
• The electronic configuration of this complex compound contains no unpaired
electron n = 0, hence it is diamagnetic.
Applications of VBT 0
CO

Ni0

CO CO

CO
Tetrahedral geometry [Ni(CO)4]0
Applications of VBT
2. Square Planar Complexes
• These are formed as a result of dsp2 hybridization.
• These are formed by strong ligands.
• E.g. are
• [Ni(CN)4]2-, [Ni(NH3)4]2+, [CO(CN)4]2-
Applications of VBT
2. Square Planar Complexes
Formation of [Ni(CN)4]2- - tetracyanonickelate (II) ion
• Ni is the central atom with Oxidation Number (ON) +2 and Co-ordination
Number (CN) is four, hence tetrahedral or square planar geometry.
• Use VBT to explain the correct geometry and the magnetic properties
3d8 4s2 4p0 4d0
i. Ni (z = 28) – [Ar] 3d84s2 n=2

ii. Ni+2 – [Ar] 3d84s0 n=2

Since CN- is a strong ligand, the
back pairing of electron in 3d
orbital and one 3d orbital is made
vacant
Applications of VBT
2. Square Planar Complexes
Formation of [NiCN4]2- - tetracyanonickelate (II) ion
• Use VBT to explain the correct geometry and the magnetic properties
iii. Ni+2 in [Ni(CN)4]2- n=0
Ni+2 undergoes dsp2 hybridization
dsp2 hybridization
iv. Hybridization Ni+2
n=0
dsp2 hybrid orbitals

v. [NiCN4]2-
n=0
CN- CN- CN- CN- diamagnetic
Applications of VBT
2. Square Planar Complexes
Formation of [Ni(CN)4]2- - tetracyanonickelate (II) ion
Conclusion
• Since this complexion is formed by dsp2 hybridization, hence it has square planar
geometry.
• The electronic configuration of this complex ion contains no unpaired electron n
= 0, hence it is diamagnetic.
Applications of VBT 2-

CN- CN-

Ni+2

CN- CN-

Square Planar Geometry of [Ni(CN)4]2-

Applications of VBT
3. Octahedral Complexes
• These are formed as a result of d2sp3 or sp3d2 hybridization.
• These are two formed by of Octahedral Complexes.
i. Inner Orbital Complexes
ii. Outer Orbital Complexes
Applications of VBT
3. Octahedral Complexes
i. Inner Orbital Complexes or spin paired or low spin complexes .
• These are formed as a result of d2sp3 hybridization in the central metal atom / ion.
• These are formed by strong ligands.
• Examples are
• K4[Fe(CN)6], K3[Fe(CN)6], [Co(NH3)6]CL3, [Co(NO3)6]3-, [Cr(NH3)6]3+ , [Cr(NO3)6]3- , [CrF6]3-
Formation of [Fe(CN)6]4- - hexacyanoferrate (II) ion
• In this complex ion, Fe is the central metal atom with oxidation number +2 (Fe+2) and
• Co-ordination number of Fe is six, the given ion has Octahedral Geometry
• Use VBT to explain the Octahedral Geometry and the magnetic properties of this
complex ion.

3d6 4s2 4p0 4d0

a. Fe (z = 26) [Ar] 3d64s2
n=4
Applications of VBT
3. Octahedral Complexes
i. Inner Orbital Complexes
Formation of [Fe(CN)6]4- - hexacyanoferrate (II) ion
b. Fe+2 [Ar] 3d64s0
n=4
Since CN- is a strong field
ligand, the black pairing of
electron in 3d orbitals so,
the two 3d orbitals are
made vacant

n=0
c. Fe+2Fein+2[Fe(CN) 6]
undergoes
4-
d2sp3 hybridization
d2sp3 hybridization

n=0

d. Hybridization in Fe+2 d2sp3 hybrid orbitals

Applications of VBT
3. Octahedral Complexes
i. Inner Orbital Complexes
Formation of [Fe(CN)6]4- - hexacyanoferrate (II) ion
e. [Fe(CN)6]4- n=0

diamagnetic
Conclusion CN- CN- CN- CN- CN- CN-
• Since this complexion ion is formed by d2sp3 hybridization, hence it has octahedral
geometry.
• The electronic configuration of this complex ion contains no unpaired electron n = 0,
hence it is diamagnetic.
• In the formation of this complex ion, the two d orbitals used in octahedral hybridization
are from the penultimate shell i.e. (n – 1) d ns and np orbitals are used in octahedral
hybridization.
• Hence it is inner orbital complex . In inner orbital complexes, there are maximum no. of
paired electron and minimum no. of unpaired electron, hence these are also known as low
spin or spin paired complexes.
Applications of VBT
CN- 4-

CN- CN-

Fe+2

CN- CN-

CN-
Octahedral Geometry of [Fe(CN)6]4-
Applications of VBT
3. Octahedral Complexes
i. Inner Orbital Complexes
Formation of [Fe(CN)6]3- - hexacyanoferrate (III) ion
• Fe is the central metal atom with oxidation number +3 and co-ordination number six.
• So it has Octahedral Geometry
• Use VBT to explain the Octahedral Geometry and magnetic properties.
3d6 4s2 4p0 4d0
a. Fe (z = 26) [Ar] 3d64s2 n=4

b. Fe+3 [Ar] 3d54s0 n=5

Since CN- is a strong ligand, the black pairing of electron in

3d orbitals, the two 3d orbitals are made vacant

n=1

Fe+3Fein [Fe(CN)
undergoes 3- d sp hybridization
+3 2 3
c. 6]
d2sp3 hybridization
Applications of VBT
3. Octahedral Complexes
i. Inner Orbital Complexes
Formation of [Fe(CN)6]4- - hexacyanoferrate (II) ion

d. Hybridization in Fe+3 n=1

d2sp3 hybrid orbitals

n=1
e. [Fe(CN)6]3- weakly paramagnetic.
CN- CN- CN- CN- CN- CN-

Conclusion
• Since this complexion ion is formed by d2sp3 hybridization, hence it has octahedral
geometry.
• The electronic configuration of this complex ion contains one unpaired electron, n = 1
hence it is weakly paramagnetic.
Applications of VBT
3. Octahedral Complexes
i. Inner Orbital Complexes
Formation of [Fe(CN)6]4- - hexacyanoferrate (II) ion
e. [Fe(CN)6]4- n=0

diamagnetic
Conclusion CN- CN- CN- CN- CN- CN-
• Since this complexion ion is formed by d2sp3 hybridization, hence it has octahedral
geometry.
• The electronic configuration of this complex ion contains no unpaired electron n = 0,
hence it is diamagnetic.
• In the formation of this complex ion, the two d orbitals used in octahedral hybridization
are from the penultimate shell i.e. (n – 1) ns and np orbitals are used in octahedral
hybridization.
• Hence it is inner orbital complex . In inner orbital complexes, there are maximum no. of
paired electron and minimum no. of unpaired electron, hence these are also known as
low spin or spin paired complexes.
Applications of VBT
CN- 3-

CN- CN-

Fe+3

CN- CN-

CN-
Octahedral Geometry of [Fe(CN)6]3-
Applications of VBT
3. Octahedral Complexes
i. Inner Orbital Complexes
Formation of [Cr(CN)6]3- - hexacyanochromate (III) ion
• Cr is the central metal atom with oxidation number +3 and co-ordination number six.
• Hence it has Octahedral Geometry
• Use VBT to explain the Octahedral Geometry and magnetic properties.
3d5 4s1 4p0 4d0
a. Cr (z = 24) [Ar] 3d54s1 n=5

b. Cr+3 [Ar] 3d34s0 n=3

Thus in Cr+3 three 3d orbitals are singly

occupied and the two are vacant. This d2sp3 hybridization
makes the possibility of d2sp3 hybridization

n=3

c. Hybridization in Cr+3 Six d2sp3 hybrid orbital

Applications of VBT
3. Octahedral Complexes
i. Inner Orbital Complexes
Formation of [Cr(CN)6]3- - hexacyanochromate (III) ion

n=3
d. [Cr(CN)6]3-
paramagnetic
CN- CN- CN- CN- CN- CN-
Conclusion
• In [Cr(CN)6]3- d2sp3 hybridization occurs so it has octahedral geometry.
• The electronic configuration contains three unpaired electrons n = , hence it is
paramagnetic.
• Note:
• Octahedral complexes of Cr+3 are always inner orbital complexes
Applications of VBT
CN- 3-

CN- CN-

Cr+3

CN- CN-

CN-
Octahedral Geometry of [Cr(CN)6]3-
Applications of VBT
3. Octahedral Complexes
ii. Outer Orbital Complexes or High Spin or Spin free Complexes
• These are formed as a result of sp3d2 hybridization in the central metal atom / ion.
• These are generally formed by weak ligands.
• Sometimes these are also formed by strong ligands in which the central metal
atom / ion has d7, d8 , d9 and d10 configuration which is unstable to make two
vacant inner d orbitals.
• Examples are
• [FeF6]3-, [CoF6]4-, [CoF6], [Cr(H2O)6]2+, [Co(NH3)6]2+ , [Ni(H2O)6]2+, [Ni(NH3)6]2+ ,
[Zn(NH3)6]2+
Applications of VBT
3. Octahedral Complexes
ii. Outer Orbital Complexes or High Spin or Spin Free Complexes
Formation of [FeF6]3- - hexafloroferrate (III) ion
• Fe is the central metal atom with oxidation number +3 and co-ordination number six.
• Hence it has Octahedral Geometry
• Use VBT to explain the Octahedral Geometry and magnetic properties.

a. Fe (z = 26) - [Ar] 3d64s2 3d6 4s2 4p0 4d0

n=4
b. Fe+3 [Ar] 3d54s0
n=5
Since F- is a weak ligand, no back pairing of
electron in 3d orbitals, so 3d orbitals can’t
be made vacant. Hence Fe+3 undergoes sp3d2 hybridization
sp3d2

c. Hybridization in Fe+3 n=5

sp3d2 hybrid orbital

Applications of VBT
3. Octahedral Complexes
ii. Outer Orbital Complexes or High Spin or Spin Free Complexes
Formation of [FeF6]3- - hexafloroferrate (III) ion

n=5
d. [FeF6]3-
highly paramagnetic
F- F- F- F- F- F-
Conclusion
• Since this complex ion is formed by sp3d2 hybridization, hence it has octahedral geometry.
• The electronic configuration of this complex ion contains five unpaired electrons n = 5,
hence it is highly paramagnetic.
• In the formation this complex ion the two d orbitals used in octahedral hybridization are
from the valence shell i.e. 4s, 4p and 4d orbitals are used, so it is outer orbital complex.
• In outer orbital complexes there are maximum number of unpaired electrons and
minimum number of unpaired electron, hence these are also known as Spin Free or high
spin Complexes
Applications of VBT
F- 3-

F- F-

Fe+3

F- F-

F-
Octahedral Geometry of [FeF6]3-
Applications of VBT
3. Octahedral Complexes
ii. Outer Orbital Complexes or High Spin or Spin Free Complexes
Formation of [Ni(NH3)6]2+ - hexa-amminenickel (II) ion
• In this complex ion Ni is the central metal atom with oxidation number +2 and co-ordination number six.
• Hence it has Octahedral Geometry
• Use VBT to explain the Octahedral Geometry and magnetic properties.

a. Ni (z = 28) [Ar] 3d84s2

3d8 4s2 4p0 4d0
b. Ni+2 [Ar] 3d84s0
n=2

n=2
Though NH3 is a strong ligand, the back
pairing of electron in 3d orbitals is not
possible. The two unpaired electrons present d2sp3 hybridization
in 3d orbitals can’t be sent to other d orbitals, which
are already completely filled. Thus two 3d orbitals
can’t be made vacant for d2sp3 hibridization. So Ni+2
undergoes sp3d2 hybridization
Applications of VBT
3. Octahedral Complexes
ii. Outer Orbital Complexes or High Spin or Spin Free Complexes
Formation of [Ni(NH3)6]2+ - hexa-amminenickel (II) ion
c. Hybridization in Ni+2 n=2
six sp3d2 hybrid orbit
n=2
d. [Ni(NH3)6]2+
paramagnetic
NH NH3 NH3 NH NH3 NH
3
- - -
3
- -
3
-

Conclusion
• It is formed by sp3d2 hybridization, hence it has octahedral geometry.
• The electronic configuration of this complex ion contains two unpaired electrons n = 2,
hence it is paramagnetic.
• It is formed by sp3d2 hybridization, hence it is outer orbital complex.
• Note
• The octahedral complexes of Ni+2 are always outer orbital complexes
Applications of VBT NH3- +2

NH3- NH3-

[Ni+2]

NH3- NH3-

NH3-
Octahedral Geometry of [Ni(NH3)6]2+
Difference Between Inner and Outer Orbital
Complexes
Inner Orbital Complexes or Low Spin or Spin Outer Orbital Complexes or High Spin or Spin
Paired Complexes free Complexes
1. These are formed by d2sp3 hybridization i.e. in 1. These are formed by sp3d2 hybridization i.e. in
the formation of six d2sp3 hybrid orbitals, two the formation of six sp3d2 hybrid orbitals, one
(n-1) d orbitals, one ns and three np orbital ns, three np and two nd orbitals are used.
are used.
2. These are generally formed by strong ligands. 2. These are generally formed by weak ligands.
3. In the formation of these complexes generally 3. In the formation of these complexes no back
back pairing of electrons in (n-1) d orbitals pairing of electrons in (n-1) d orbitals.
takes place.
4. These are generally diamagnetic sometimes 4. These are generally paramagnetic sometimes
weak paramagnetic. diamagnetic.
5. These complexes have comparatively lesser 5. These complexes have comparatively greater
number of unpaired electrons and hence are number of unpaired electrons and hence are
also called low spin or spin paired complexes. also called high spin or spin free complexes.
Limitations of Valence Bond Theory (VBT)
• Valence Bond Theory fairly explain the geometry and the magnetic
properties of the complexes.
• But it can’t explain the following
1. The absorption spectra or the colour formation of the complexes.
2. The relative stabilities for different shapes of complexes.
3. The nature of ligands (strong field or weak field).
4. Why did different complexes of same metal show different colours.
5. The rates of reactions of the complexes.
6. The detail properties is explained on the basis of number of unpaired
electrons.
Applications of Complex Compounds
• The complex compounds as well as the complex formation techniques
are used in different fields.
• Some of the major applications of co-ordination compounds are given
below.
1. For the estimation of hardness of water:
 The hardness of water is estimated by titrating the hard water with EDTA.
 EDTA forms a stable complexes with Ca+2 and Mg+2 ions present in hard
water.
2. In qualitative analysis:
 The complex formation techniques are used in qualitative analysis to
separate the salt from the mixture of salts.
 The solution containing Cu+2 and Cd+2 ions an exerts of KCN solution is
added.
Applications of Complex Compounds
2. In qualitative analysis:
 The KCN dissociates in the solution to give CN- ions which form cyano complexes with
both the ions i.e. [Cu(CN)4]2- and [Cd(CN)4]2-.
 On passing H2S through the solution Cd complex gets precipitated as cadmium
sulphide CdS due to its larger solubility.
3. In metallurgy:
 The complex formation techniques are used in metallurgy for the extraction of metals
from their ores.
 In extraction of Ag from Ag2S in cyanide process by complexing Ag+ with CN- in
accordance with the reaction.
Ag2S + 4NaCN 2Na[Ag(CN)2] + Na2S
Sodium argentocyanide
 The metallic silver is recovered by treating the solution of Na[Ag(CN)2] with zinc dust.
2Na[Ag(CN)2] + Zn Na2 [Zn(CN)4] + 2Ag
Applications of Complex Compounds
4. For softening water:
 The hardness of water is removed by permutit and calgon process.
 The permutit and calgon are complex compounds.
5. In electroplating:
 The complex compounds are generally used as an electrolyte for the
electroplating of metals.
 This is due to the following reasons
a. Complexes are more stable towards oxidation, reducing hydrolysis, in solution
than the simple ions.
b. Complexes give a controlled supply of metal ions in the solution. This is
because the complexes are more stable and they dissociate to very small
extent as a result the concentrations of free metal ions in the solution give
better deposit during electroplating. Na[Ag(CN)2] and Na[Au(CN)2] are
generally used in electroplating of Ag and Au respectively.
Applications of Complex Compounds
6. As a catalyst:
 Most of the complex compounds are used in the catalyst in many organic
reactions. Co2(CO)8 cobalt carbonyl is used as a catalyst for the conversion
of olefins (c =) to alcohol
7. As dyeing:
 The complex compounds are used as a mordant in dyeing industries.
8. In the field of medicine:
 Complexes have been found useful in the treatment of certain diseases.
 For example
o The platinum complex, cis[Pt(NH3)2 Cl2] known as cis-platinum has been found
useful in cancer chemotherapy
Applications of Complex Compounds
9. In nature:
 Most of the naturally occurring biological substances are complex
compounds.
 Chlorophyll is a complex of Mg+2 with porphyrin.
 Haemoglobin is a complex of Fe+2 with porphyrin.
 Vitamin B12 is complex of Co+2