Issue 1, 2006

Electronic structures of trans-dioxometal complexes

Abstract

We have employed computational methods based on density functional theory to elucidate the effects of equatorial ligands on the electronic structures of trans-dioxometal complexes. In complexes with ammine (σ-only) equatorial donors, the 1A1 g(b2 g)21Eg(b2 g)1(eg)1 excitation energy increases with metal oxidation state: Mo(IV) < Tc(V) < Ru(VI) and W(IV) < Re(V) < Os(VI). Increasing transition energies are attributed to enhanced oxometal π-donor interactions in the higher valent central metals. But in complexes with cyanide equatorial donors, the 1A1 g(b2 g)21Eg(b2 g)1(eg)1 energy remains roughly independent of metal oxidation state, likely owing to the compensating increased π-donation from the π(CN) orbitals to the metal dxy orbitals as the oxidation state of the metal increases.

Graphical abstract: Electronic structures of trans-dioxometal complexes

Article information

Article type
Paper
Submitted
30 Aug 2005
Accepted
10 Oct 2005
First published
04 Nov 2005

Dalton Trans., 2006, 168-171

Electronic structures of trans-dioxometal complexes

P. Hummel, J. R. Winkler and H. B. Gray, Dalton Trans., 2006, 168 DOI: 10.1039/B512299F

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