Evidence for a charge-transfer intermediate in the catalytic epoxidation of alkenes by ruthenium complexes: a comparison between electrochemical and kinetic data
F. Maran et al., Evidence for a charge-transfer intermediate in the catalytic epoxidation of alkenes by ruthenium complexes: a comparison between electrochemical and kinetic data, INORG CHIM, 288(1), 1999, pp. 122-125
The catalytic oxidation of various olefins by iodosobenzene in the presence
of the diphosphino complexes of ruthenium(II) [RuCl(LL)(2)]PF6, where LL i
s 1,3-bis(diphenylphosphino)propane (DPP) or 1-diphenylphosphino-2-(2'-pyri
dyl)ethane (PPY), gives rise to epoxides, obeying the Michaelis-Menten kine
tic law. The calculated kinetic parameters (K-m) follow a free energy corre
lation with the one-electron oxidation potentials of the olefins, measured
in the reaction conditions, thus suggesting that the reaction intermediate
of the epoxidation is substantially charge-transfer in character. (C) 1999
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