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
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 Δ
– 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
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
Spectrochemical series (strength of ligand interaction)

Increasing 

Cl- < F- < H2O < NH3 < en < NO2- < CN-

Increasing 
As Energy difference increases, electron configuration
changes
“Low spin”
“High spin”

Co(III) is d6
Square planar complexes are different still
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, Δtet should be smaller than

the Δoct (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)
 Tetrahedral Complexes
In tetrahedral complexes, orbitals are inverted.
Again because of orientation of orbitals and ligands

 is always small, always low spin (less ligands)

 Ligand Field Stabilization Energy
The first row transition metals in water are
all weak field, high spin cases.

do d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
LFSE 0 .4Δo .8 1.2 .6 0 .4 .8 1.2 .6 0
 Experimental Evidence for LFSE
The hydration energies of the first row
transition metals should increase across the
period as the size of the metal ion gets
smaller.

M2+ + 6 H2O(l)  M(H2O)62+

Experimental Evidence for LFSE
The heats of
hydration show two
“humps” consistent
with the expected LFSE
for the metal ions.
The values for d5 and
d10 are the same as
expected with a LFSE
equal to 0.
 Experimental Evidence of LFSE
do d1 d2 d3 d4 d5 d6 d7 d 8 d9 d10
LFSE 0 .4Δo .8 1.2 .6 0 .4 .8 1.2 .6 0
 High Spin vs. Low Spin
3d metals are generally high spin complexes
except with very strong ligands. CN- forms low
spin complexes, especially with M3+ ions.

4d & 4d metals generally have a larger value of

∆o than for 3d metals. As a result, complexes
are typically low spin.
• Teori Orbital Molekul

• Ikatan terjadi karena adanya LCAO

Molecular orbital descriptions of dioxygen species.
Molecular orbital approach to bonding in octahedral complexes, ML6

______________________________________________________________________________________________________________________________

Combinations of atomic orbitals Molecular Orbital

4s ± 1/√6(σ1 + σ2 + σ3 + σ4 + σ5 + σ6) a1g

4px ± 1/√2 (σ1  σ2)

4py ± 1/√2 (σ3  σ4) t1u
4pz ± 1/√2 (σ5  σ6)

3dx2 - y2 ± 1/2 (σ1 + σ2  σ3  σ4) eg

3dz2 ± 1/√12 (2 σ5 + 2 σ6  σ1  σ2  σ3  σ4)

3dxy
3dxz Non-bonding in σ complex t2g
3dyz
_______________________________________________________________________________________________
MO diagram for s-bonded octahedral metal complex
 M.O. Diagram for Tetrahedral Metal Complex

Since the metal 4p and t2 orbitals are of the same symmetry, e → t2 transitions in
Td complexes are less “d-d” than are t2g → eg transitions in Oh complexes. They are
therefore more allowed and have larger absorbtivity values (e)
 Metal-ligand P-bonding interactions

 t2g orbitals (dxy, dxz, dyz) are non-bonding in a s-bonded octahedral

complex

 ligands of P-symmetry overlap with the metal t2g orbitals to form

metal-ligand P-bonds.

 P-unsaturated ligands such as CO, CN- or 1,10-phenanthroline or sulfur

and phosphorus donor ligands (SR2, PR3) with empty t2g-orbitals have
the correct symmetry to overlap with the metal t2g orbitals.
 π Bonding
The main source of π bonding is between
the dxy, dyz and dxz orbitals on the metal and
the d, p or π* orbitals on the ligand.
 π Bonding
The ligand may have empty d or π* orbitals
and serve as a π acceptor ligand, or full p or d
orbitals and serve as a π donor ligand.
 Pacceptor interactions have the effect of lowering the energy of
the non-bonding t2g orbitals and increasing the magnitude oct.

This explains why P-acceptor ligands like CO and CN- are strong field ligands, and
why metal carbonyl and metal cyanide complexes are generally low-spin.
P-interactions involving P-donation of electron density from filled p-
orbitals of halides (F- and Cl-) and oxygen donors, to the t2g of the
metal, can have the opposite effect of lowering the magnitude of
oct. In this case, the t2g electrons of the s-complex, derived from the
metal d orbitals, are pushed into the higher t2g* orbitals and become
antibonding. This has the effect of lowering oct.

Ligand p (full)
M L e.g. halide ion, X-
RO-

Metal- d (t2g) Ligand - p

Effect of ligand to metal Pdonor interactions
 π Bonding
The empty π antibonding orbital on CO can
accept electron density from a filled d orbital
on the metal. CO is a pi acceptor ligand.

filled d empty π*
orbital orbital
P-alkene organometallic complexes

Zeise’s Salt, K[PtCl3(C2H4)]

 Pacceptor interactions have the effect of lowering the energy of
the non-bonding t2g orbitals and increasing the magnitude oct.

This lowering of the energy of the t2g orbitals also results in 9 strongly bonding
M.O.’s well separated in energy from the antibonding orbitals
 π Donor Ligands (LM)
All ligands are σ donors. Ligands with filled
p or d orbitals may also serve as pi donor
ligands. Examples of π donor ligands are I-, Cl-,
and S2-. The filled p or d orbitals on these ions
interact with the t2g set of orbitals (dxy, dyz and
dxz) on the metal to form bonding and
antibonding molecular orbitals.
π Donor Ligands (LM)
The bonding orbitals,
which are lower in
energy, are primarily
filled with electrons from
the ligand, the and
antibonding molecular
orbitals are primarily
occupied by electrons
from the metal.
π Donor Ligands (LM)
The size of ∆o
decreases, since it is now
between an antibonding
t2g orbital and the eg*
orbital.
This is confirmed by
the spectrochemical
series. Weak field ligands
are also pi donor ligands.