Proton-Coupled O-Atom Transfer in the Oxidation of HSO3- by the Ruthenium Oxo Complex trans-[RuVI(TMC)(O)2]2+ (TMC = 1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane)

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

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Author(s)

  • Qian Wang
  • Po-Kam Lo
  • William W. Y. Lam

Related Research Unit(s)

Detail(s)

Original languageEnglish
Pages (from-to)12699-12702
Journal / PublicationInorganic Chemistry
Volume56
Issue number21
Online published13 Oct 2017
Publication statusPublished - 6 Nov 2017

Abstract

We have previously reported that the oxidation of SO32- to SO42- by a trans-dioxoruthenium(VI) complex, [RuVI(TMC)(O)2)]2+ (RuVI TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazcyclotetradecane) in aqueous solutions occurs via an O-atom transfer mechanism. In this work, we have reinvestigated the effects of the pH on the oxidation of SIV by RuVI in more detail in order to obtain kinetic data for the HSO3- pathway. The HSO3- pathway exhibits a deuterium isotope effect of 17.4, which indicates that O-H bond breaking occurs in the rate-limiting step. Density functional theory calculations have been performed that suggest that the oxidation of HSO3- by RuVI may occur via a concerted or stepwise proton-coupled O-atom transfer mechanism.

Citation Format(s)

Proton-Coupled O-Atom Transfer in the Oxidation of HSO3- by the Ruthenium Oxo Complex trans-[RuVI(TMC)(O)2]2+ (TMC = 1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane). / Wang, Qian; Zhao, Hong Yan; Lo, Po-Kam; Lam, William W. Y.; Lau, Kai-Chung; Lau, Tai-Chu.

In: Inorganic Chemistry, Vol. 56, No. 21, 06.11.2017, p. 12699-12702.

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