Stoichiometric and catalytic oxidations of alkanes and alcohols mediated by highly oxidizing ruthenium-oxo complexes bearing 6,6'-dichloro-2,2'-bipyridine

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journal

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Detail(s)

Original languageEnglish
Pages (from-to)7996-8000
Journal / PublicationJournal of Organic Chemistry
Volume65
Issue number23
Publication statusPublished - 17 Nov 2000

Abstract

The ruthenium(II) complex cis-[Ru(6,6'-Cl2bpy)2(OH2)2](CF3SO3)2 (1) is a robust catalyst for C-H bond oxidations of hydrocarbons, including linear alkanes, using tert-butyl hydroperoxide (TBHP) as terminal oxidant. Alcohols can be oxidized by the '1 + TBHP' protocol to the corresponding aldehydes/ketones with high product yields at ambient temperature. Oxidation of 1 with Ce(IV) in aqueous solution affords cis-[Ru(VI)(6,6'-Cl2bpy)2O2]2+, which is isolated as a green/yellow perchlorate salt (2). Complex 2 is a powerful stoichiometric oxidant for cycloalkane oxidations under mild conditions. Oxidation of cis-decalin is highly stereoretentive; cis-decalinol is obtained in high yield, and formation of trans-decalinol is not observed. Mechanistic studies showing a large primary kinetic isotope effect suggest a hydrogen-atom abstraction pathway. The relative reactivities of cycloalkanes toward oxidation by 2 have been examined through competitive experiments, and comparisons with Gif-type processes are presented.

Citation Format(s)

Stoichiometric and catalytic oxidations of alkanes and alcohols mediated by highly oxidizing ruthenium-oxo complexes bearing 6,6'-dichloro-2,2'-bipyridine. / Che, C. M.; Cheng, K. W.; Chan, M. C W; Lau, T. C.; Mak, C. K.

In: Journal of Organic Chemistry, Vol. 65, No. 23, 17.11.2000, p. 7996-8000.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journal