Laporte Rule

In a molecule or ion possessing center of symmetry, transitions are not allowed

between orbitals of same parity. Transitions are only possible between orbitals that
differ by Δl = ±1; ‘l’ is the orbital quantum number.

Examples of forbidden transitions are: s to s, d to d, p to f etc.

Tetrahedral geometry is not affected by this rule as it does not have a center of
symmetry.
As a consequence, ε for tetrahedral complexes are 100 times more than the ε for
octahedral complexes.

Even octahedral complexes lose their center of symmetry transiently due to

unsymmetrical vibrations. This leads to color in octahedral and square planar
complexes
 Spin-forbidden and Spin-allowed Transitions

Any transition for which ΔS≠0 is strongly forbidden; that is, in order to be allowed, a
transition must involve no change in spin state.

Allowed Forbidden

[Mn(H2O)6]2+ has a d5 metal ion and is a high-spin complex. Electronic transitions are
not only Laporte-forbidden, but also spin-forbidden. The dilute solutions of Mn2+
complexes are therefore colorless.
However, certain complexes such as MnO4-, CrO42- etc are intensely colored even
though they have metal ions without electrons in the d orbitals. The color of these
complexes are not from d-d transitions, but from charge-transfer from ligand to metal
orbitals.
Charge Transfer bands: In a charge‐transfer transition (CT) an electron is moved between 
orbitals that are predominantly ligand in character and orbitals that are predominantly 
metal in character. The transition is classified as a ligand to metal charge transfer transition 
(LMCT transition) if the migration of the electron is from the ligand to the metal. 
LMCT: KMnO4 
In some complexes, metal to ligand charge transfer transition (MLCT). 
MLCT: tris(bipyridyl)iron(II).

LMCT transition: The color of CdS ‘cadmium yellow’ is due to the transi on Cd2+ (5s) ← S2‐

(p). Similarly HgS is red as a result of the transi on Hg2+ (6s) ← S2‐ (p) and in iron oxides 
(red and yellow) by the transi on Fe(3d) ← O2‐ (p). 
The tetraoxoanions of metals with high oxidation number provide what are probably the 
most familiar examples of LMCT bands. In them, an O lone pair electron is promoted into a 
low lying empty metal orbital. High metal oxidation states corresponds to a low d‐orbital 
population so the acceptor level is available and low in energy. 

Ligand to metal transitions are observed: 
1.When the metal is in a high oxidation state 
2.Ligands contain lone pair of electrons 
MLCT transitions: Metal to ligand are most commonly observed in complexes with 

1. Ligands that have low lying p* orbitals, especially aromatic ligands. 

2. The transition will occur at low energy if the metal ion has low oxidation number. 

The family of ligands most commonly involved in MLCT transitions are diimines, which have 
two N donor atoms: 2,2’‐bipyridine and 1,10‐ phennanthroline. Complexes of tris(2,2’‐
bipyridyl)Ru(II), which is orange on account of its MLCT band, this complex is a versatile 
photochemical redox reagent. 
 d0 and d10 ions have no d-d transitions

Zn2+ d10 ion  white

TiF4 d0 ion white
TiCl4 d0 ion white
TiBr4 d0 ion orange
TiI4 d0 ion dark brown

[MnO4]‐ Mn(VII) d0 ion extremely purple

[Cr2O7]‐ Cr(VI) d0 ion  bright orange

[Cu(MeCN)4]+ Cu(I) d10 ion  colourless

[Cu(phen)2]+ Cu(I) d10 ion  dark orange
Problem Solving
 Magnetic Properties of Coordination Complexes

Diamagnetic Compounds: Those, which tend to move out of a magnetic field.

Example: N2

Paramagnetic Compounds: Those, which tend to move into a magnetic field.

Example: O2

The extent of paramagnetism is measured in terms of the magnetic moment, μ. The

larger the magnitude of μ, greater the paramagnetism of the compound.

Magnetic moment has contributions from spin and orbital angular momentum. A non-
spherical environment may lead to quenching of the contribution from orbital angular
momentum.

However, the spin-only magnetic moment survives in all cases and is related to the total
number of unpaired electrons.

μeff = μs.o = 2√S(S+1) = √n(n+2) BM

 Magnetic Properties of Coordination Complexes
μeff = 2√S(S+1) = √n(n+2) BM

If there is a possibility for contribution from the orbital angular momentum,

μ = √L(L+1) + 4S(S+1)

For a given value of the orbital quantum number l, the magnetic quantum number m
can have any values from –l to +l and L = sum of m

For d orbital electrons, m = 2, 1, 0, -1, -2

If there is only one electron in the d orbitals, L = 2
 Magnetic Properties of Coordination Complexes

x 45º x

y y
d xy d x 2-y 2

z 90º z

y y
d yz dxz
For an octahedral complex, orbital contributions are possible only when the t2g orbitals
are differentially occupied and for a tetrahedral complex the t2 orbitals have to be
differentially occupied.
 Magnetic Properties of Coordination Complexes

K3[Fe(CN)6] has a magnetic moment of 2.3 B.M., which is a d5 low-spin complex with
one unpaired electron.
[Fe(H2O)6]3+ ions are high-spin with 5 unpaired electrons. It has a magnetic moment of
6 B.M.
 Magnetic Properties of Coordination Complexes
Consider a Ni(II) complex, electronic configuration is d8
For a free metal ion,

S = 1, L = 3 and μ = √L(L+1) + 4S(S+1) = 4.47 B.M.

For an octahedral complex,

Orbital contribution is zero and

magnetic moment is close to the spin
only value

For a tetrahedral complex,

Magnetic moment is higher than the

spin only value as there is positive
orbital contribution
 Magnetic Properties of Coordination Complexes

Co(II) d7
K2CoCl4 [Co(H2O)6]Cl2

moisture
Blue Pink
heat

t
o

No orbital contribution
Magnetic moment µ = 3.73 BM
Orbital contribution
Magnetic moment µ = 4.2 B.M.
higher than spin-only value
Problem Solving