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Issue 1, 2006
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Electronic structures of trans-dioxometal complexes

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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

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Publication details

The article was received on 30 Aug 2005, accepted on 10 Oct 2005 and first published on 04 Nov 2005


Article type: Paper
DOI: 10.1039/B512299F
Citation: Dalton Trans., 2006, 168-171
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    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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