Mechanism of C-H bond oxidation by a monooxoruthenium(V) complex

Research output: Journal Publications and ReviewsRGC 22 - Publication in policy or professional journal

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Author(s)

  • Chi-Ming Che
  • Clare Ho
  • Tai-Chu Lau

Detail(s)

Original languageEnglish
Pages (from-to)1259-1263
Journal / PublicationJournal of the Chemical Society, Dalton Transactions
Issue number5
Publication statusPublished - 1991
Externally publishedYes

Abstract

The complex [RuvL(O)]2+ {HL = [2-hydroxy-2-(2-pyridyl)ethyl]bis[2-(2-pyridyl)ethyl]amine} was found to be a very active stoichiometric oxidant towards various hydrocarbons. Oxidation of alcohols was studied either in 0.1 mol dm-3 HClO4 or CH3CN, the observed rate law being rate = k[Ruv][alcohol]. The second-order rate constants for various alcohols follow the order benzylic > secondary > primary alcohols. Kinetic isotope effects (kH/kD) of 5.9 and 5.3 were found for benzyl alcohol and PriOH respectively. Similar kinetic studies for the oxidation of tetrahydrofuran gave kH/kD = 6.8. Stoichiometric oxidation of saturated alkanes in acetonitrile gave tertiary alcohols exclusively or ketones when only methylene groups are present. The measured kH/kD for the oxidation of cyclohexane determined from competitive oxidation experiments was 5.3. No cyclohexyl chloride was found when the oxidation of cyclohexane was carried out in the presence of CCl4. The mechanism of C-H bond oxidation by Ruv=O is discussed.

Citation Format(s)

Mechanism of C-H bond oxidation by a monooxoruthenium(V) complex. / Che, Chi-Ming; Ho, Clare; Lau, Tai-Chu.
In: Journal of the Chemical Society, Dalton Transactions, No. 5, 1991, p. 1259-1263.

Research output: Journal Publications and ReviewsRGC 22 - Publication in policy or professional journal