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L16 PDF

1. Selection rules dictate which electronic transitions are allowed in coordination complexes. The Laporte selection rule forbids transitions between states of the same parity, while the spin selection rule forbids transitions between states of different spin multiplicities. 2. Vibronic coupling and spin-orbit coupling can relax the selection rules by temporarily changing the symmetry or mixing spin states. 3. Tanabe-Sugano diagrams correlate the electronic states of octahedral complexes and are used to determine spectroscopic splitting parameter Δo and Racah parameter B from absorption spectra.

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432 views14 pages

L16 PDF

1. Selection rules dictate which electronic transitions are allowed in coordination complexes. The Laporte selection rule forbids transitions between states of the same parity, while the spin selection rule forbids transitions between states of different spin multiplicities. 2. Vibronic coupling and spin-orbit coupling can relax the selection rules by temporarily changing the symmetry or mixing spin states. 3. Tanabe-Sugano diagrams correlate the electronic states of octahedral complexes and are used to determine spectroscopic splitting parameter Δo and Racah parameter B from absorption spectra.

Uploaded by

Umar Jutt
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Selection rules

1. Laporte selection rule


Transition between states of the same parity are
forbidden. e.g., g  u allowed; g  g forbidden
Relaxation mechanism:
a. Vibronic coupling – vibration may temporarily change
the symmetry to relax the first selection rule.
d-d transitions, having molar absorptivity in the range
of 5-50 L mol–1 cm–1, occurs exhibiting the colors.
b. mixing of p-orbital character with d-orbital character

1
Selection rules
2. Spin selection rule
Transition between states of different spin multiplicities
are forbidden. e.g., 4A2  4T1 spin-allowed; 4A2  2A2
spin-forbidden
Relaxation: spin-orbit coupling may relax the second
selection rule as allowing transitions between different
spin multiplicity. For the 1st row transition metals, very
weak (<1 L mol–1 cm–1), more important for 2nd , 3rd
transition metals.

2
Correlation diagrams

3
Tanabe-Sugano diagrams
The ground
electronic state is
always plotted
along the horizontal
axis. This makes it
easy to determine
values of E/B above
the ground state.
Example [V(H2O)6]3+ (d2)
Three spin-allowed transitions
for d2 configuration:
Tanabe-Sugano diagrams for d2, d3, d8
Tanabe-Sugano diagrams for d4 – d7
Determining Δo from spectra using T-S diagram
First approximations of Δo values, B by using the positions
of the absorption from spectra (depends on d-electron
configuration), sometimes directly deduced from spectrum
Example [V(H2O)6]3+ (d2)
Two absorption bands at
17,800 and 25,700 cm–1.
Estimate values of Δo, B
Example [V(H2O)6]3+ (d2)
Example Co(II) (d7) Two absorption bands at
16,000 cm–1 for 4T1g  4A2g,
20,000 cm–1 for 4T1g (4F)  4T1g
(4P)
Tetrahedral complexes
More intense absorptions than octahedral complexes as a
result of the first (Laporte) selection rule (lack of center of
symmetry in Td).
Hole formalism:

In practical terms, we can use the correlation diagram for


the d10-n configuration of Oh geometry to describe the dn
configuration of Td geometry
Charge transfer
Very intense, responsible for the vivid colors of halogens in
donor solvents. X2·donor → [donor+][X2–]
Molar absorptivity (ε) > ~50,000 L mol–1 cm–1, much more
intense than d-d transitions (ε < ~20 L mol–1 cm–1).
Ligand to metal charge transfer (LMCT), resulting formal
reduction of metal. e.g., IrBr63– (d6)
Charge transfer
Metal to ligand charge transfer (MLCT), resulting in
oxidation of metal, found in coordination complexes
having π-acceptor (empty π* orbital)ligands (CO, CN–,
SCN–, bipyridine, dithiocarbamate)

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