Alkene cis-dihydroxylation by [(Me3tacn)(CF3CO2)RuVIO2]CIO4(Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane): Structural characterization of [3 + 2] cycloadducts and kinetic studies

Wing Ping Yip, Wing Yiu Yu, Nianyong Zhu, Chi Ming Che

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Abstract

cis-Dioxoruthenium(VI) complex [(Me3tacn)(CF3CO2)RuVIO2]CIO4(1, Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) reacted with alkenes in aqueous tert-butyl alcohol to afford cis-1,2-diols in excellent yields under ambient conditions. When the reactions of 1 with alkenes were conducted in acetonitrile, oxidative C=C cleavage reaction prevailed giving carbonyl products in >90% yields without any cis-diol formation. The alkene cis-dihydroxylation and C=C cleavage reactions proceed via the formation of a [3 + 2] cycloadduct between 1 and alkenes, analogous to the related reactions with alkynes [Che et al. J. Am. Chem. Soc. 2000, 122, 11380], With cyclooctene and trans-β-methylstyrene as substrates, the Ru(III) cycloadducts [(Me3tacn)(CF3CO2)RuIIIO(H)CH(CH2)6HCO]CIO4(4a) and [(Me3tacn)(CF3CO2)RuIIIO(H)-PhCHCH(CH3)O]CIO4(4b) were isolated and structurally characterized by X-ray crystal analyses. The kinetics of the reactions of 1 with a series of p-substituted styrenes has been studied in acetonitrile by stopped-flow spectrophotometry. The second-order rate constants varied by 14-fold despite an overall span of 1.3 V for the one-electron oxidation potentials of alkenes. Secondary kinetic isotope effect (KIE) was observed for the oxidation of β-d2-styrene (kH/kD= 0.83 ± 0.04) and α-deuteriostyrene (kH/kD= 0.96 ± 0.03), which, together with the stereoselectivity of cis-alkene oxidation by 1, is in favor of a concerted mechanism.
Original languageEnglish
Pages (from-to)14239-14249
Number of pages11
JournalJournal of the American Chemical Society
Volume127
Issue number41
DOIs
Publication statusPublished - 19 Oct 2005
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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