Organic Products from Oxidation of Metal Carbynes

Lisa McElwee-White

doi:10.1055/s-1996-5585

Synlett 1996; 1996(9): 806-814
DOI: 10.1055/s-1996-5585

account

© Georg Thieme Verlag, Rüdigerstr. 14, 70469 Stuttgart, Germany. All rights reserved. This journal, including all individual contributions and illustrations published therein, is legally protected by copyright for the duration of the copyright period. Any use, exploitation or commercialization outside the narrow limits set by copyright legislation, without the publisher's consent, is illegal and liable to criminal prosecution. This applies in particular to photostat reproduction, copying, cyclostyling, mimeographing or duplication of any kind, translating, preparation of microfilms, and electronic data processing and storage.

Organic Products from Oxidation of Metal Carbynes

Lisa McElwee-White^*

^*Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200, USA, Fax: (352) 846-0296; Internet: lmwhite@chem.ufl.edu

Abstract

PDF Download All articles of this category

Photooxidation of the metal carbyne complexes (η⁵-C₅H₅)-L₁L₂M≡CR [M = Mo, W; L₁, L₂ = CO, P(OMe)₃; R = aryl, alkyl] generates radical cations that are extremely reactive. Depending on the reaction conditions and the carbyne substituent, the radical cation either exhibits the ligand exchange and atom abstraction processes that are typical of metal radicals or the carbyne ligand undergoes rearrangement to yield organic products such as olefins, dienes, cycloalkenones and dienals. The formation of organic products is triggered by H-abstraction at the carbyne carbon of the radical cation to yield a cationic carbene complex. For certain reactions, cationic carbene complexes can also be accessed by protonation, providing a mechanistic link between the photooxidation and acid-induced reactions of metal carbynes.

metal carbynes - photooxidation - metal radicals - 17 e^- complex

PDF (837 kb)