T. Crevier, J. Mayer
Sep 10, 1997
Citations
0
Influential Citations
17
Citations
Journal
Journal of the American Chemical Society
Abstract
Reactions of alcohols with WCl2(PMe3)4 (1) or WH2Cl2(PMe3)4 (2) yield W(O)Cl2(PMe3)3 (3), PMe3, and hydrocarbons. Cyclopropanemethanol is deoxygenated to give 1-butene and a trace of trans-2-butene as the organic products; benzyl alcohol yields toluene and bibenzyl. These products indicate the intermediacy of organic radicals. Benzyl radicals in the reaction of 1 with PhCH2OH can be trapped by added 2 or by 9,10-dihydroanthracene (DHA), leading to increased yields of toluene vs bibenzyl. With WD2Cl2(PMe3)4 (2-d2) or DHA-d12, PhCH2D is formed. The reaction of methanol with 1 proceeds similarly in the presence of DHA, forming 3 and methane. Kinetic studies on the reaction of 1 with benzyl alcohol indicate that the reaction proceeds via alkoxide intermediates. A mechanism involving homolysis of the C−O bond in an alkoxide intermediate is suggested by these results. The thermodynamics of this unusual transformation are discussed.