4-ELECTRON REDUCTION OF DIAZO-COMPOUNDS AT A SINGLE TUNGSTEN METAL CENTER - A THEORETICAL-STUDY OF THE MECHANISM

Authors
MASERAS F LOCKWOOD MA EISENSTEIN O ROTHWELL IP
Citation
F. Maseras et al., 4-ELECTRON REDUCTION OF DIAZO-COMPOUNDS AT A SINGLE TUNGSTEN METAL CENTER - A THEORETICAL-STUDY OF THE MECHANISM, Journal of the American Chemical Society, 120(26), 1998, pp. 6598-6602
Citations number
26
Categorie Soggetti
Chemistry
Journal title
Journal of the American Chemical Society → ACNP
ISSN journal
00027863
Volume
120
Issue
26
Year of publication
1998
Pages
6598 - 6602
Database
ISI
SICI code
0002-7863(1998)120:26<6598:4RODAA>2.0.ZU;2-U
Abstract
A possible mechanism for the unprecedented one-metal reduction of diaz obenzene by the [W(OC6HPh3-eta(6)-C6H5)(OAr)(PMe2Ph)] (OAr = 2,3,5,6-t etraphenyloxide) complex was characterized by hybrid Becke3LYP DFT cal culations on the model system [W(OH)(2)(C6H6)(Ph-3)]+ N2H2 The model r eaction is shown to be strongly exothermic, and takes place via a mult istep process with moderate activation energy barriers. We discuss how this specific set of ancillary ligands permits the reaction to occur on a one-metal system in place of the more usual two-metal systems.