Teori Ikatan

Senyawa koordinasi
Valence bond Theory (hybridization)
A set of hybrid orbitals is produced to explain the
bonding.
Octahedral d2sp3 (6 hybrid orbitals of equal energy)
Tetrahedral - ??
Uses inner and outer orbitals to explain the
experimentally determined unpaired electrons.
The magnetic behavior determines which d orbitals
(e.g. 3d or 4d) are used for bonding (Figure 10-2).
Valence bond Theory (hybridization)
A set of hybrid orbitals is produced to explain the
bonding.
Octahedral d2sp3 (6 hybrid orbitals of equal energy)
Tetrahedral - ??
Uses inner and outer orbitals to explain the
experimentally determined unpaired electrons.
The magnetic behavior determines which d orbitals
(e.g. 3d or 4d) are used for bonding (Figure 10-2).
 Valence Bond Description

Two configurations are possible for d4-d7 ions.

Fe(III) has 5 electrons in the d-orbitals.
One unpaired electron, the ligands are strong and force the
metal d electrons to pair up.
Strong-field (bind strongly) low spin complex
The hybridization orginates from the 3d inner orbitals (d2sp3).
Five unpaired electrons, the ligands are weak and cannot
force the metal d electrons to pair up.
Weak-field (bind weakly) high spin
The hybridization originates from the 4d outer orbitals (sp3d2).
 Crystal Field Theory
Focus: energies of the d orbitals

Assumptions
1. Ligands: negative point
charges
2. Metal-ligand bonding: entirely ionic

strong-field (low-spin): large splitting of d orbitals

weak-field (high-spin): small splitting of d orbitals
[V(H2O)6]2+ [V(H2O)6]3+

[Cr(NH3)6]3+ [Cr(NH3)5Cl]2+s
Ligand field splitting
1. The ligand field splitting depends upon the metal,
the oxidation state of the metal, and the ligand type
2. High oxidation state favors large
Mn2+ < Ni2+ < Co2+ < Fe2+ < V2+ < Fe3+ < Co3+ <
Mn4+ <
Mo3+ < Rh3+ < Ru3+ < Pd4+ < Ir3+ < Pt4+
3.Effect of ligand is given by the spectrochemical
series
I- < Br- < S2- < SCN- < Cl- < NO3- < F- < OH- <
C2O42- < H2O< NCS- < CH3CN < NH3 < en < bipy <
phen < NO2- < PPh3 <CN- < CO
Tetrahedral complexes
Three of the d-orbitals point almost towards the ligands.
The other two point between the ligands
Repulsion between the ligand electrons and electrons in the three
d-orbitals that almost point at the ligands destabilizes them

For a given ligand-metal combination, tet should be smaller than

the oct (4/9ths) as there are fewer ligands in the tetrahedral
complex and none of them point directly at the d-orbitals
20_459

Tetrahedral Complexes

dz 2 dx2 y2

dxy dxz dyz

(a) (b)
20_461

Square Planar & Linear Complexes

dx2 - y2
dz2

E
E dxy dxz dyz
dz2
dxy dx2 - y2
dxz dyz
Free metal ion Complex
Free metal ion Complex

M
M z
y
(a) (b)

Approach along x-and y- Approach along z-axis

axes