TY - JOUR
T1 - Inner-sphere electron transfer in metal-cation chemistry
AU - Schröder, Detlef
AU - Trage, Claudia
AU - Schwarz, Helmut
AU - Danovich, David
AU - Shaik, Sason
PY - 2000/12/25
Y1 - 2000/12/25
N2 - 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.
AB - 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.
KW - Electron transfer
KW - Metal ions
KW - Potential-energy surfaces
KW - Reaction mechanisms
KW - Transition metals
UR - http://www.scopus.com/inward/record.url?scp=0034716199&partnerID=8YFLogxK
U2 - 10.1016/S1387-3806(00)00349-3
DO - 10.1016/S1387-3806(00)00349-3
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AN - SCOPUS:0034716199
SN - 1387-3806
VL - 200
SP - 163
EP - 173
JO - International Journal of Mass Spectrometry
JF - International Journal of Mass Spectrometry
IS - 1-3
ER -