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Electronic structures of trans-dioxometal complexes

Hummel, Patrick and Winkler, Jay R. and Gray, Harry B. (2006) Electronic structures of trans-dioxometal complexes. Dalton Transactions, 2006 (1). pp. 168-171. ISSN 1477-9226. https://resolver.caltech.edu/CaltechAUTHORS:HUMdt06

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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)^2 → Eg(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)^2 →Eg(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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1039/b512299fDOIUNSPECIFIED
ORCID:
AuthorORCID
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Additional Information:© The Royal Society of Chemistry 2005 Received 30th August 2005, Accepted 10th October 2005. First published on the web 4th November 2005
Issue or Number:1
Record Number:CaltechAUTHORS:HUMdt06
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:HUMdt06
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:6899
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:01 Jan 2007
Last Modified:22 Nov 2019 09:58

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