Electronic absorption spectra

Selection rules
Electronic transitions that occur without change in number
of unpaired electrons (spin multiplicity) are allowed
Electronic transitions that involve a change in the number
of unpaired spins are forbidden and are therefore of low
intensity.
> e.g., solutions of high-spin d5, e.g., Mn(II), complexes
are lightly colored

Allowed vs forbidden transitions

dx2-y2 dz2 dx2-y2 dz2

E dxz dxy dyz dxz dxy dyz

dx2-y2 dz2 dx2-y2 dz2

dxz dxy dyz dxz dxy dyz

 Number of d electrons and spectral intensity

[Mn(OH2)6]2+

Electronic absorption spectra

Electronic transitions are symmetry forbidden in

complexes with a center of symmetry (octahedral), but are
not symmetry forbidden in complexes without a center of
symmetry (tetrahedral)

Comparison of electronic absorption

Comparison of electronic absorption
spectral intensities for [Mn(OH2)6]2+
spectral intensities for [Co(OH2)6]2+
and [MnBr4]2- (symmetry)
and [CoCl4]2- (symmetry)
 Electronic absorption spectra, contd
Absorption bands are broad because metal-ligand bonds are
constantly changing distance (vibration) and since electronic
transitions occur faster than atomic motions this means that
there are effectively many values of o.
d0 and d10 complexes do not have d-d transitions and are
colorless unless there are other types of absorptions with
energies that fall in the visible region
Ph
Base
Ph

N N
N N
Ph Zn Ph + Base Ph Zn Ph
N N N N

Ph
Ph

d1 and d9, and high-spin d4 and d6 ions have only one spin-
allowed transition; high-spin d2, d3, d7 and d8 have three spin-
allowed transitions

Variation of )O in octahedral Ti(III) complexes

Ti(III) is a d1 ion and exhibits one absorption in the electronic

spectrum of its metal complexes due to transition of the electron
from the t2g (lower energy) orbitals to the eg (higher energy)
orbitals. The energy of the absorption corresponds to )O.

Ligand )O/cm-1*
Br- 11,400
Cl- 13,000
(H2N)2C=O 17,550
NCS- 18,400
F- 18,900
H2O 20,100
CN- 22,300
*E = h< = hc/8
 Transitions in d1 and d2 complexes

dx2-y2 dz2

dxz dxy dyz

dx2-y2 dz2 dx2-y2 dz2

dxy1 dx2-y21 dxz1dz21 dyz1dz21
dx2-y2 dz2
E
dxz dxy dyz dxz dxy dyz dxz1 dx2-y21 dxy1dz21 dyz1dx2-y21
dxz dxy dyz

dx2-y2 dz2 dx2-y2 dz2

dxz dxy dyz dxz dxy dyz

Some compounds are very highly colored

because of charge transfer transitions even
some with no d electrons
There can be electronic transitions in the visible region that do
not involved d-electrons
MnO4- (purple) and CrO42- (yellow) are intensely colored
because electrons in filled oxygen based orbitals are
excited into empty d-orbitals (LMCT)
Ligand to Metal Charge Transfer (LMCT) bands have few
selection rule restrictions and are typically very intense
Metal to Ligand Charge Transfer (MLCT) bands may also occur
for complexes with d-electrons.
There are few selection rules and the high intensity of these
bands may mask d-d transitions.
Crystal field splitting in tetrahedral complexes
Tetrahedral arrangement of four ligands
showing their orientation relative to the
Cartesian axes and the dyz orbital.
The orientation with respect to dxz, dxz and
dxy is identical and the interaction with
these orbitals is considerably greater than
with the dz2 and dx2- y2 orbitals; therefore
the dyz, dxz and dxy orbitals are higher in
energy than dz2 and dx2- y2 .
Because there are only four ligands and
the ligand electron pairs do not point
directly at the orbitals, t ~4/9 o. As a
result the spin-pairing energy is always
greater than and tetrahedral complexes
are always high spin.

Comparison of crystal field splittings for

octahedral, square planar and tetrahedral
ligand fields
Factors affecting the magnitude of ) (Crystal
Field Splitting)

Charge on the metal. For first row transition elements )O varies from
about 7,500 cm-1 to 12,500 cm-1 for divalent ions and 14,000 cm-1 to
25,000 cm-1 for trivalent ions.
Position in a group. )O values for analogous complexes of metal ions
in a group increase by 25% to 50% on going from one transition series
to the next. This is illustrated by the complexes [M(NH3)6]3+ where )
values are 23,000 cm-1 for M=Co; 34,000 cm-1 for M=Rh and 41,000
cm-1 for M=Ir.
Geometry and coordination number. For similar ligands )t will be
about 4/9 )O. This is a result of the reduced number of ligands and
their orientation relative to the d orbitals. Recall that the energy
ordering of the orbitals is reversed in tetrahedral complexes relative to
that in the octahedral case.
Identity of the ligand. The dependence of ) on the nature of the
ligand follows a regular order, known as the spectrochemical series, for
all metals in all oxidation states and geometries.