期刊
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
卷 200, 期 1-3, 页码 163-173出版社
ELSEVIER SCIENCE BV
DOI: 10.1016/S1387-3806(00)00349-3
关键词
electron transfer; metal ions; potential-energy surfaces; reaction mechanisms; transition metals
Bond activation of organic molecules by metal cations is usually rationalized either in terms of the chemistry of Lewis acids or via oxidative addition of metal fragments to R-X bonds, that is, R-X+M+-->R-M+-X--> products. In most of these mechanisms, the positive charge is assumed to be located on the metal center. Here, we propose an alternative mechanism, to which we refer as inner-sphere electron transfer (ET). Thus, provided that certain conditions are fulfilled, the insertion species R-M+-X may isomerize via ET to [R+ ... MX] structures with the positive charge located mostly at the organic residue R. If R-M+-X and [R+ ... MX] are not just resonance structures but distinct minima on the related potential-energy surfaces, there also exists a transition structure between the two, that is, an ET-TS. Here, the role of inner sphere ET in organometallic gas-phase reactions and the possible existence of ET-TSs are discussed for a series of examples investigated both computationally and experimentally. (C) 2000 Elsevier Science B.V.
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