Kinetics of alkene oxidation by cationic trans-dioxoruthenium(VI) complexes. Effect of driving force on rate constants

Chi Ming Che; Chi Keung Li; Wai Tong Tang; Wing Yiu Yu

doi:10.1039/DT9920003153

Kinetics of alkene oxidation by cationic trans-dioxoruthenium(VI) complexes. Effect of driving force on rate constants

Chi Ming Che, Chi Keung Li, Wai Tong Tang, Wing Yiu Yu

Research output: Journal article publication › Journal article › Academic research › peer-review

40 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	3153-3158
Number of pages	6
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	21
DOIs	https://doi.org/10.1039/DT9920003153
Publication status	Published - 1 Dec 1992
Externally published	Yes

ASJC Scopus subject areas

General Chemistry

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10.1039/DT9920003153

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title = "Kinetics of alkene oxidation by cationic trans-dioxoruthenium(VI) complexes. Effect of driving force on rate constants",

abstract = "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.",

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AU - Che, Chi Ming

AU - Li, Chi Keung

AU - Tang, Wai Tong

AU - Yu, Wing Yiu

PY - 1992/12/1

Y1 - 1992/12/1

N2 - 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.

AB - 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.

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Kinetics of alkene oxidation by cationic trans-dioxoruthenium(VI) complexes. Effect of driving force on rate constants

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