The kinetics of alkene oxidation by a series of isostructural trans-dioxoruthenium(VI) complexes with E°(RuVI-RuV) ranging from 0.23 to 0.7 V vs. saturated calomel electrode has been investigated in acetonitrile. The experimental rate law is rate = k2[RuVI][alkene]. A linear free-energy relationship between log k2and E°(RuVI-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 k2versus σ+for the para substituents with a ρ value of -2.1 was found. A charge-transfer mechanism alone is insufficient to explain the experimental findings.
|Number of pages||6|
|Journal||Journal of the Chemical Society, Dalton Transactions|
|Publication status||Published - 1 Dec 1992|
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