The kinetics of alkene oxidation by a series of isostructural trans-dioxoruthenium(vi) complexes with E0(RuV'-RuV) ranging from 0.23 t o 0.7 V vs. saturated calomel electrode has been investigated in acetonitrile. The experimental rate law is rate = k2[RuV'] [alkene]. A linear free-energy relationship between log kz and E0(RuV'-Ruv) for the oxidation of styrene and norbornene has been observed. Both steric and electronic effects of alkenes as well as the E" of the dioxoruthenium(vi) complexes affect the rate constants. For the oxidation of para-substituted styrenes, a linear Hammett plot of log kz versus 0 ' for the para substituents with a p value of -2.1 was found. A charge-transfer mechanism alone is insufficient to explain the experimental findings.
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