Notes. Oxo transfer reactions. Mechanistic studies on the oxidation of triphenylphosphine by trans-[ RuVIL(O)2]2+ (L = 1,4,8,11 -tetramethyl- 1,4,8,11 -tetra-azacyclotetradecane)

Chi Ming Che, Kwok Yin Wong

Research output: Journal article publicationJournal articleAcademic researchpeer-review

Abstract

The mechanism for the oxidation of PPh3 to O=PPh3 by trans- [ RuVIL(O)2]2+ (L = 1,4,8,11- tetramethyl- 1,4,8,11 -tetra-azacyclotetradecane) in CH3CN was studied from 280 to 299 K. The rate law for the reaction is d [RuVI]/dt = k2[PPh3] [RuVI]. At 299 K, k2, is (1.28 ± 0.1) × 102 dm3 mol-1 s-1. The ΔH‡ and ΔS‡ values are (8.7 ± 0.8) kcal mol-1 and -20 ± 2 cal K-1 mol-1 respectively. A direct comparison between the reactivities of trans-[RuVI(O)2]2+ and [RuIV(bipy)2(py)(O)]2+ (bipy = 2,2′- bipyridine; py = pyridine) towards the oxidation of PPh3 shows the ruthenium(IV) complex to react 1 000 times faster.
Original languageEnglish
Pages (from-to)2065-2067
Number of pages3
JournalJournal of the Chemical Society, Dalton Transactions
Issue number10
DOIs
Publication statusPublished - 1 Jan 1989
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)

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