VALENCE BOND THEORY FOR

COORDINATION CHEMISTRY

Setia Budi
Jurusan Kimia, Universitas Negeri Jakarta

Valence bond theory

The formation of coordination compounds involves reaction between
Lewis bases (ligands) and Lewis acid (Central atom) with the formation
of coordinate covalent bond
A set of hybrid orbitals is produced to explain the bonding
[Ag(CN)2]- , based on experimental result, has bonding angle of 180 oC

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s, p and d orbitals

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Orbitals hybridization
Hybridization: Linear combination of
atomic orbitals on an atom
(goldbook-IUPAC), to form new hybrid
orbitals suitable for the qualitative
description of atomic bonding
properties

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Hybrid orbitals
sp

[Ag(CN)2]-

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Hybrid orbitals
sp2
[Cu(CN)3]2-

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Hybrid orbitals
sp3
[CoCl4]2-

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Example 4: [NiCl4]2, tetrahedral

Ni2+ [Ar] 3d8

3d

4s

4p
4sp3
paramagnetic

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Hybrid orbitals
dsp2
[Cu(NH3)4]2+

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Example 3: [PtCl4]2, diamagnetic

Pt2+ [Xe] 4f14 5d8
5d

6s

6p

dsp2
square planar

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Hybrid orbitals
sp3d
[SnCl5]2-

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Hybrid orbitals
sp3d2
[Fe(H2O)6]2+

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Example 1: [Co(NH3)6]3+
Co [Ar] 3d7 4s2
Co3+ [Ar] 3d6
Inner orbital complex

3d

4s

4p

4d

d2sp3
octahedral
Diamagnetic complexes
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Example 2: [CoF6]3
Co [Ar] 3d7 4s2
Co3+ [Ar] 3d6
Outer orbital complex

3d

4s

4p

4d

4sp3d2
octahedral
Paramagnetic complexes
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Electroneutrality principle

Electroneutrality principle expresses the tendency of all pure substances to carry a net
charge of zero
Complexes would be most stable when the electronegativity of the ligand was such that
the metal achieved a condition of essentially zero net electrical charge.
One difficulty with the VB assumption of electron donation from ligands to metal ions is
the build up of formal negative charge on the metal

An example: [CoL6 ]2+, a complex of Co(II)

The six ligands share twelve electrons with the metal atom, thereby contributing to the
formal charge on the metal a total of 6, which is only partially canceled by the metal's
ionic charge of + 2
From a formal charge point of view, the cobalt acquires a net 4 charge.
Pauling pointed out why metals would not in fact exist with such unfavorable negative
charges
the bonding electrons will not be shared equally between the metal and ligands due to
the high electronegative of donor atoms on ligands (e.g. N, O and the halogens)

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Electroneutrality principle
Explain briefly of the following fact:
[Be(H2O)4 ]2+ is stable, while [Be(H2O)6]2+ is not.
[AI(H2O)6 ]3+ is more stable than [AI(NH3)6]3+.

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Back bonding
Opposite to the electroneutrality principle,
Many complexes in which the metal exists in a low oxidation state and yet is
bonded to an element of fairly low electronegativity.
CO is the prominent ligand for such complex
When central atom is bound to atom carbon in the ligand, the source of
stability in these complexes is the capacity of the carbon monoxide ligand to
accept a "back donation" of electron density from the metal atom (described in
term of resonance)

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Magnetic properties of Complexes

In 1845, Michael Faraday classified substances as diamagnetic and

paramagnetic
Diamagnetic effect is generated by paired .
When any diamagnetic complex is placed in an external magnetic field,
there is an induced circulation of producing a net magnetic moment
aligned in opposition to the applied field.

Paramagnetism is generated by unpaired .

The spin and orbital motions of these give rise to permanent
molecular magnetic moments that tend to align themselves with an
applied field.
Paramagnetic effect is much larger than diamagnetic effect.
Consequently it cancels any repulsion between an applied field and
paired .
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Magnetic susceptibility balance

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Magnetic properties of Complexes

Dalam atom, elektron bergerak mengorbit
inti atom dan berotasi di sekitar sumbu
sumbu rotasinya
Apabila 2 elektron berpasangan maka 1
elektron melakukan rotasi berlawanan
arah dengan putaran jarumnya dan
pasanganya beortasi dengan arah
sebaliknya
Rotasi yang arahnya berlawanan jarum
jam akan menghasilkan momen magnet
yang arahnya ke bawah dan berlaku
sebaliknya untuk elektron pasangannya
Momen magnet yang dihasilkan adalah
sama besar, sehingga momen magnet
pasangan elektron adalah nol
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 Momen magnetik terukur yang dimiliki oleh suatu kompleks disebut

momen magnetik efektif (e)
e yang dimiliki suatu komplek merupakan hasil interaksi dari momen
magnetik yang ditimbulkan akibat gerak mengorbit dan gerak rotasi dari
elektron dalam atom
e = 0, diamagnetik (ditolak oleh medan magnetik eksternal)
e > 0, paramagnetik (ditarik oleh medan magnetik eksternal)
Momen magnetik yang dihasilkan oleh gerak mengorbit elektron sangat
kecil dibandingkan dengan momen magnetik dari gerak rotasi
Momen magnetik yang hanya ditimbulkan dari gerak rotasi disebut
momen magnetk spin (s) dengan satuan Magneton Bohr (BM)
s = [n(n+2)]1/2
n = jumlah elektron tak berpasangan pada atom pusat kompleks
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Kelemahan Teori Ikatan Valensi

Tidak dapat menjelaskan warna atau spektra
senyawa kompleks
Tidak dapat menjelaskan kestabilan senyawa
kompleks
Tidak dapat menjelaskan bentuk geometri dari
[Cu(NH3)4]2+
dll

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