20.

9A: The Nephelauxetic Effect

The spectra of the aqua ions for some first row transition metal ions are shown below.

For a much more detailed description of the interpretation of the spectra of first row transition metal ion complexes see
the notes on the use of Tanabe-Sugano diagrams.

Cr(III) - an example in more detail

For \9d^3\), d octahedral and
8
d
2
, d
7
tetrahedral complexes, the above diagrams can be used to interpret the observed
electronic absorption spectra.

Figure 2
Take for example the Cr aquo-ion [Cr(H O) ] . From the simplified Orgel diagram in Figure 2, three absorptions
3 +
2 6
3 +

transitions are expected. In practice, the spectrum is found to contain three bands which occur at 17,000 cm-1, 24,000 cm-1
and 37,000 cm-1. Of which only two are shown in Figure 1.
μ1 corresponds exactly to Δ (Delta) and since the lowest band is found at 17,000 cm-1 then this enables us to measure Δ
directly from the spectrum.
The next band is found at 24,000 cm-1 and this can be equated to:
μ = 9/5Δ − x (20.9A.1)
2

where x is the configuration interaction between the T(F) state and the T(P) state of the same symmetry.
Since Δ is 17,000 and μ2 is observed at 24,000 then x must be 6,600 cm-1.
The last band is seen at 37,000 cm-1 and here
μ3 = 6/5Δ + 15B + x (20.9A.2)

where B is one of the RACAH parameters.

Solving Equation 20.9A.2 for B gives a value of B = 667 cm −1
.
For the free Cr3+ ion, B is ~1030 cm-1 so that in the complex this term is reduced by ~2/3 of the free ion value.
A large reduction in B indicates a strong Nephelauxetic Effect. The Nephelauxetic Series is given by:
− − − − − − − −
F > H O > urea > NH > en\~ C O > NCS > Cl  CN > Br > S2  I (20.9A.3)
2 3 2 42

Ionic ligands such as F give a small reduction in B , while covalently bonded ligands such as I give a large reduction of
− −

B.

Contributors
Prof. Robert J. Lancashire (The Department of Chemistry, University of the West Indies)

Robert J. Lancashire 4/18/2020 20.9A.1 https://chem.libretexts.org/link?34406