Spectrochemical series

A spectrochemical series is a list of ligands ordered on ligand strength and a list of metal ions based on oxidation number, group and its identity. In crystal field theory, ligands modify the difference in energy between the d orbitals (Δ) called the ligand-field splitting parameter for ligands or the crystal-field splitting parameter, which is mainly reflected in differences in color of similar metal-ligand complexes.

Spectrochemical series of ligands

A partial spectrochemical series listing of ligands from small Δ to large Δ is given below.   (for a table, see the ligand page)

I⁻ < Br⁻ < S²⁻ < SCN⁻ < Cl⁻ < NO₃⁻ < N₃⁻ < F⁻ < OH⁻ < C₂O₄²⁻ ≈ H₂O < NCS⁻ < CH₃CN < py (pyridine) < NH₃ <en (ethylenediamine) < bipy (2,2'-bipyridine) < phen (1,10-phenanthroline) < NO₂⁻ < PPh₃ < CN⁻ ≈ CO

Ligands arranged on the left end of this spectrochemical series are generally regarded as weaker ligands and cannot cause forcible pairing of electrons within 3d level and thus form outer orbital octahedral complexes. On the other hand ligands lying at the right end are stronger ligands and form inner orbital octahedral complexes after forcible pairing of electrons within 3d level.^[1]

However, keep in mind that "the spectrochemical series is essentially backwards from what it should be for a reasonable prediction based on the assumptions of crystal field theory."^[2] This deviation from crystal field theory highlights the weakness of crystal field theory's assumption of purely ionic bonds between metal and ligand.

Spectrochemical series of metals

The metal ions can also be arranged in order of increasing Δ, and this order is largely independent of the identity of the ligand.^[3]

Mn²⁺ < Ni²⁺ < Co²⁺ < Fe²⁺ < V²⁺ < Fe³⁺ < Cr³⁺ < V³⁺ < Co³⁺

In general, it is not possible to say whether a given ligand will exert a strong field or a weak field on a given metal ion. However, when we consider the metal ion, the following two useful trends are observed:

• Δ increases with increasing oxidation number, and
• Δ increases down a group.^[3]

See also

• Nephelauxetic effect

References

• Zumdahl, Steven S. Chemical Principles Fifth Edition. Boston: Houghton Mifflin Company, 2005. Pages 550-551 and 957-964.

• D. F. Shriver and P. W. Atkins Inorganic Chemistry 3rd edition, Oxford University Press, 2001. Pages: 227-236.

• James E. Huheey, Ellen A. Keiter, and Richard L. Keiter Inorganic Chemistry: Principles of Structure and Reactivity 4th edition, HarperCollins College Publishers, 1993. Pages 405-408.