Splitting of d-orbitals in Tetrahedral field

Tetrahedral case is completely different from Octahedral

 The approach of the ligands is in between the axis instead of along the axis as was
in the case of the octahedral complexes .


• Metal ion at the center and ligands

occupying four alternate corners of the cube
thus rest four corners of the cube are empty.
•The orientation of two ‘eg’ set of orbitals is
towards center of the face of the cube and
the three ‘t2g’ orbitals point to the center of
the edges of the cube.
•The angle of metal and ligand in eg orbital is
one-half of the tetrahedral angle, i.e. 109o28’
/ 2 = 54o44’.
•The angle between the t2g-orbitals, metal
and ligand is one-third of the tetrahedral
angle, i.e. 109o28’ / 3 = 35o16’.
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Splitting of d-orbitals in Tetrahedral field

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 Tetrahedral vs Octahedral crystal field
Since the number of ligands in the case of tetrahedral complexes is two less as
compared to the octahedral ones, the splitting parameter of the former is also less.
The ligand field is roughly 2/3 of the octahedral field. The direction of approach of in
tetrahedral complex does not coincide with the d-orbitals. This reduces the field by
2/3. Therefore Δt is roughly 2/3 x 2/3 = 4/9 of Δo. Where ∆t is the splitting parameter
of the tetrahedral complexes.

All the tetrahedral

complexes formed are
high spin in nature
irrespective of the
splitting parameter
because the value of ∆t
is small to such an
extent that it is always
less than the value of
pairing energy.

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Crystal field stabilization energy for tetrahedral complexes
The CFSE value in the case of tetrahedral complexes can be calculated by using the
relation
CFSE(Td) = (–0.6x + 0.4y ) Δt + mP
Where x and y represent the no of electrons in the lower eg and the upper t2g level
and m is no of electron pairs present in both the levels

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Splitting of d-orbitals in Square Planar complexes
Formed when two ligands on the z-axis of an octahedron are removed from the
complex,
 As the z-ligands move away, the ligands in the square plane move a little closer to
the metal.

As ligands move away along the z-axis, d-orbitals with a z-component will fall in
energy. The dz2 orbital falls the most, as its electrons are concentrated in lobes along
the z-axis. The dxz and dyz orbitals also drop in energy, but not as much. Conversely,
the dx2-y2 and the dxy orbitals increase in energy. The splitting diagram for square
planar complexes is more complex than for octahedral and tetrahedral complexes,
and is shown below with the relative energies of each orbital.

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Crystal Field Stabilization Energy in Square Planar Complexes
Square planar coordination is rare except for d8 metal ions. Among the d8 metal
ions exhibiting square planar coordination are nickel(II), palladium(II), platinum(II),
rhodium(I), iridium(I), copper(III), silver(III), and gold(III). Copper(II) and silver(II),
both d9 ions, are occasionally found in square planar coordination .
All known square planar complexes of d8 ions are diamagnetic, because the
highest-energy orbital (dx2-y2) is greatly destabilized, and pairing in the dxy orbital is
more favorable than placing an unpaired electron in the dx2-y2 orbital.

The crystal field stabilization energy for a diamagnetic

square planar d8
metal complex is readily calculated by the usual method:

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FACTOR'S AFFECTING MAGNITUDE OF CFSE
Magnitude of CFSE depends upon the following factors.
1. Nature of the Central Metal ion
2. Nature of the Ligand
3. Geometry of the complex
Nature of the Metal Ion:
a. Oxidation state of the metal:
Complexes having same geometry and Same ligands , the value of ∆
increases with increase in oxidation states.
[Fe(H2O)6]2+ - 9400 cm-1

[Fe(H2O)6]3+ - 14000 cm-1

Reason: Due to substantial increase in σ- bonding which is due to decrease in radius of
the metal ion having higher oxidation states.
b. Δo increases as the metal changes from 3d < 4d < 5d:
Co [Co(NH3)6]3+ 22870 cm-1
Rh [Rh(NH3)6]3+ 34000 cm-1
Ir [Ir(NH3)6]3+ 41200 cm-1
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FACTOR'S AFFECTING MAGNITUDE OF CFSE (CONTD.)
Nature of Ligand
weak field ligand (I-) small Δo
strong field ligand (CN-) large Δo

“ Series of ligands arranged in increasing order of their splitting power is known as

spectrochemical series.

The value of ∆increases with increasing oxidation number of the central metal ion. The
variation of oxidation number reflects the smaller size of more highly charged ions and
consequently shorter metal-ligand distances and stronger interaction energies. The value of
∆ increases down the group. This reflects the larger size of the 4d and 5d orbitals compared
with the compact 3d orbitals and the consequent stronger interaction of the ligands.
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FACTOR'S AFFECTING MAGNITUDE OF CFSE (CONTD.)
Geometry of the complex

orbitals)

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