Bonding in Coordination Complexes

1. Presented by
Dr. Neelam
Department of chemistry

2. BONDING IN COORDINATION COMPOUNDS
Werner's Theory :
According to Werner's : Each metal in coordination compound possesses two types of
valencies
(i) primary valency or principal
valencies or ionisable
valencies
(ii) Secondary valency or non
ionisable valencies
 It is satisfied by anions only.
 It shows oxidation state of the central
metal.
 It is non-directional
 These are represented by dotted lines
(-------) between central metal atom and
anion.
It is satisfied only by electron pair donor,
the ions or the neutral species.
 secondary valencies also referred as
coordination number.
 It is directional
 These are represented by thick lines
valencies

3. Alfred Werner (considered as the father of coordination chemistry) studied the
structure of coordination complexes such as CoCl3. 6NH3 in 1893. According to
him-

4. [Co(NH3)5Cl]Cl2
[Co(H2 O)5Cl]Cl2

5. Effective Atomic Number Rule given by Sidgwick :
It can be defined as the resultant number of electrons with the metal
atom or ion after gaining electrons from the donor atoms of the ligands.
Effective Atomic Number (EAN) = No. of electron present on the metal
atom/ion + No. of electrons donated by ligands to it.
OR
Effective Atomic Number (EAN) = Atomic no. of central metal-
Oxidation state of central metal + No. of electrons donated by ligands.
EAN = Z- Oxi. No. + no. of e- of ligand
The complexes in which the EAN of the central atom equals the atomic
number of the next noble gas, are found to be extra stable.

6. [Fe(CN)6] 2+[Co(H2 O)6] 3+
EAN = 9 + 2 x 6 -3
= 18
EAN = 27 – 3 + 2 x 6
= 36
EAN = 8 + 2 x 6 -2
= 18
EAN = 26 + 2 x 6 -2
= 36
[Ni(C O)4]
EAN = 10 + 2 x 4
= 18
EAN = 28 + 2 x 4
= 36

7. The valence bond theory, VBT, was extended to coordination compounds by Linus
Pauling in 1931.
According to this theory, the formation of a coordinate-covalent (or dative) bonds
between metal & ligand.
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
geometry such as octahedral, tetrahedral, square planar.
M L
Empty orbitals Filled orbital of ligand

8. magnetic properties of complexes
Paramagnetic : unpaired electrons
Diamagnetic : paired electrons
magnetic moment :
Octahedral complex
Inner orbital complex outer orbital complex
d2sp3 hybridisation sp3d2 hybridisation
Low spin complex high spin complex
Tetrahedral complex sp3 hybridisation
Square planer complex dsp2 hybridisation

9. Thus, the complex has octahedral geometry and is
diamagnetic because of the absence of unpaired electron.
d2sp3 hybridisation
inner orbital or low spin or spin paired complex.
Spin magnetic moment = 0
The complex [Co(NH3)6]3+, the cobalt ion is in +3 oxidation state and has the
electronic configuration represented as shown below.

10. The complex [FeF6]4– is paramagnetic and uses outer orbital (4d) in
hybridisation (sp3d2 ) ; it is thus called as outer orbital or high spin or spin
free complex.
Thus, the complex has octahedral geometry and is
paramagnetic because of the absence of unpaired electron.
sp3d2 hybridisation
outer orbital or high spin complex.
Spin magnetic moment = 4.9 BM

11. Limitations of Valence Bond Theory
While the VB theory, to a larger extent, explains the formation, structures and
magnetic behaviour of coordination compounds, it suffers from the following
shortcomings:
(i) It involves a number of assumptions.
(ii) It does not give quantitative interpretation of magnetic data.
(iii) It does not explain the colour exhibited by coordination compounds.
(iv) It does not give a quantitative interpretation of the thermodynamic or kinetic
stabilities of coordination compounds.
(v) It does not make exact predictions regarding the tetrahedral and square planar
structures of 4-coordinate complexes.
(vi) It does not distinguish between weak and strong ligands.

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