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Bonding in coordination compounds

VALENCE BOND THEORY


Effective atomic number (EAN) rule : based on
the octet theory of Lewis this is the first attempt to
account for the bonding in complexes
The formation of a complex was described as an
acid - base reaction according to Lewis
The sum of the electrons on the central atom (Lewis
acid) including those donated from the ligands
(Lewis base) should be equal to the number of
elctrons on a noble gas
Prof. Dr. Fakhili Gul

Prof. Dr. Fakhili Gul

Complex geometry can be linked to five


main orbital hybridization processes.

Valence bond theory


Valence Bond Theory predicts metal complex bonding arises
from overlap of filled ligand orbitals and vacant metal orbitals.

CN
2

Resulting bond is a coordinate covalent bond.

Prof. Dr. Fakhili Gul

Hybrid Orbitals in Octahedral Ion

Hybrid
orbitals

Geometry

Example
[Ag(NH3)2]+

Linear

sp

Trigonal

sp2

Tetrahedral

sp3

[CoCl4]2-

Square planar

dsp2

[Ni(CN)4]2

Trigonal bipyramids dsp3

Octahedral

d2sp3 or
sp3d2

[Cr(H2O)6]3+,
[Co(H2O)6]2+

Prof. Dr. Fakhili Gul

Hybrid Orbitals in Square Planar Ion

Prof. Dr. Fakhili Gul

Prof. Dr. Fakhili Gul

Tetrahedral geometry

Hybrid Orbitals in Tetrahedral Ion


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[CoCl4 ]2

Tetrahedral complex
3d

4p

4s

Co ground
state

Co2+

sp3
4 e pairs by Cl ions

Gives [CoCl4]2 three unpaired electrons, which makes it


paramagnetic and attracted by magnets.
Prof. Dr. Fakhili Gul

Prof. Dr. Fakhili Gul

Square Planar Geometry

Octahedral sp3d2 Geometry

[Ni(CN)4 ]2

3d

4s

Gives [CoF6]3 four unpaired electrons, which makes it


paramagnetic and is called a high-spin complex.

4p

Ni

3d

Ni2+

4s

4p

4d

Co3+

[Ni(CN)4 ]

[CoF6]3-

dsp2

sp3d2

Gives [Ni(CN)4]2 all paired electrons, which makes it


diamagnetic and weakly repelled by magnets.
Prof. Dr. Fakhili Gul

Prof. Dr. Fakhili Gul

Octahedral d2sp3 Geometry

sp3d2 and d2sp3 hybrids

[Fe(CN)6 ]3

The difference between sp3d2 and d2sp3 hybrids lies in the


principal quantum number of the d orbital.

Fe+3

In sp3d2 hybrids, the s, p, and d orbitals have the same


principal quantum numberHigh Spin.

[Fe(CN)6 ]3

In d2sp3 hybrids, the principal quantum number of the d


orbitals is one less than that of s and p orbitalsLow Spin.

A complexs magnetic properties determine which hybrid is


being used.

3d

CN

Strong ligand

4s

d2sp3

4p

(Inner orbital complex)


Prof. Dr. Fakhili Gul

Prof. Dr. Fakhili Gul

Magnetic behaviour

Illustrative Example
Discuss the geometry of the compound [Cr(CO)6].
Solution

3d

4s

4p

4s

4p

Ground state Cr
3d

Excited state Cr(0)

Hybridization state
Electrons donated by
ligand 'CO'

M = n(n + 2)
Where n is the number of unpaired electrons
Prof. Dr. Fakhili Gul

d2sp3 hybridization
octahedral
geometry
Prof. Dr.=
Fakhili
Gul

Illustrative Example

Solution contd.

Discuss the geometry of [PtCl4]2- and [NiCl4]2- .


Solution:

Geometry of

Ground state Pt

[PtCl4]2-

2+

5d

6s

Excited state Pt

2+

5d

6s

Ground state Ni

6p

Geometry of [NiCl4]22+

3d

4s

4p

Hybridization state

6p

Electrons donated by
ligand '4Cl- '

Hybridization state

Electrons donated by
ligand '4Cl- '

sp3 hybrid = tetrahedral.

dsp2 hybrid = square planar.


Prof. Dr. Fakhili Gul

Prof. Dr. Fakhili Gul

Illustrative Example

Solution contd.

[Co(NH3)6]3+ is diamagnetic and [CoF6]3- is paramagnetic.


Explain with the help of valence bond theory.
Solution
3+

4s

4s

3d

4p

4p

[CoF6]36

3+

3d

4s

4p

Ground state Co

Ground state Co

3+

3d

Excited state Co

4s

4p

4d

Hybridization state

Hybridization state

Electrons donated by
ligand '6F- '

Electrons donated by
ligand '6NH3'

Prof. Dr. Fakhili Gul

Prof. Dr. Fakhili Gul

Crystal Field Theory

Crystal Field Theory


Consider bonding in a complex to be an
electrostatic attraction between a positively
charged nucleus and the electrons of the
ligands.
Electrons on metal atom repel electrons
on ligands.
Focus particularly on the d-electrons on
the metal ion.
Prof. Dr. Fakhili Gul

Prof. Dr. Fakhili Gul

Crystal Field Theory


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Focus: energies of the d orbitals


Assumptions

1. Ligands: negative point charges


2. Metal-ligand bonding: entirely ionic
3. strong-field (low-spin): large splitting
of d orbitals
4. weak-field (high-spin): small splitting
of d orbitals
Prof. Dr. Fakhili Gul

22

20_454

eg(d z2, d x 2 y 2)

t2g (d xz, d yz, d xy)

= crystal field
splitting

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Free metal ion


3d orbital
energies
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High spin

Low spin
25

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Tetrahedral Complexes
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dz2

dxy
(b)

(a)

dx2 y2

dxz

dyz

Prof. Dr. Fakhili Gul

27

Square Planar & Linear Complexes


dx2 - y2

dz2
E

dxy
dz2
Free metal ion

dxz
dyz
Complex

Free metal ion

dxz

dyz

dxy

dx2 - y2

Complex

x
M
M

y
(a)

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Approach along x-and y-axes

(b)

Approach along z-axis

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