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

Publication Date:
31 December 2000 (online)

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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

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