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)

Qian Wang; Hong Yan Zhao; Po-Kam Lo; William W. Y. Lam; Kai-Chung Lau; Tai-Chu Lau

doi:10.1021/acs.inorgchem.7b02509

Author(s)

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

Related Research Unit(s)

Department of Chemistry

Detail(s)

Original language	English
Pages (from-to)	12699-12702
Journal / Publication	Inorganic Chemistry
Volume	56
Issue number	21
Online published	13 Oct 2017
Publication status	Published - 6 Nov 2017

Link(s)

DOI	DOI https://doi.org/10.1021/acs.inorgchem.7b02509 Final Published version
	Check@CityULib
Link to Scopus	https://www.scopus.com/record/display.uri?eid=2-s2.0-85033403368&origin=recordpage
Permanent Link	https://scholars.cityu.edu.hk/en/publications/publication(f32e575c-32c0-4859-b569-32e737c1764d).html

Abstract

We have previously reported that the oxidation of SO₃^2- to SO₄^2- by a trans-dioxoruthenium(VI) complex, [Ru^VI(TMC)(O)₂)]²⁺ (Ru^VI 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 S^IV by Ru^VI 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 Ru^VI may occur via a concerted or stepwise proton-coupled O-atom transfer mechanism.

Citation Format(s)

[ RIS ] [ BibTeX ]

Proton-Coupled O-Atom Transfer in the Oxidation of HSO₃^- by the Ruthenium Oxo Complex trans-[Ru^VI(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 journal › peer-review

Wang, Q, Zhao, HY, Lo, P-K, Lam, WWY, Lau, K-C & Lau, T-C 2017, 'Proton-Coupled O-Atom Transfer in the Oxidation of HSO₃^- by the Ruthenium Oxo Complex trans-[Ru^VI(TMC)(O)₂]²⁺ (TMC = 1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane)', Inorganic Chemistry, vol. 56, no. 21, pp. 12699-12702. https://doi.org/10.1021/acs.inorgchem.7b02509

Wang, Q., Zhao, H. Y., Lo, P-K., Lam, W. W. Y., Lau, K-C., & Lau, T-C. (2017). Proton-Coupled O-Atom Transfer in the Oxidation of HSO₃^- by the Ruthenium Oxo Complex trans-[Ru^VI(TMC)(O)₂]²⁺ (TMC = 1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane). Inorganic Chemistry, 56(21), 12699-12702. https://doi.org/10.1021/acs.inorgchem.7b02509

Wang Q, Zhao HY, Lo P-K, Lam WWY, Lau K-C , Lau T-C. Proton-Coupled O-Atom Transfer in the Oxidation of HSO₃^- by the Ruthenium Oxo Complex trans-[Ru^VI(TMC)(O)₂]²⁺ (TMC = 1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane). Inorganic Chemistry. 2017 Nov 6;56(21):12699-12702. https://doi.org/10.1021/acs.inorgchem.7b02509

Wang, Qian ; Zhao, Hong Yan ; Lo, Po-Kam ; Lam, William W. Y. ; Lau, Kai-Chung ; Lau, Tai-Chu. / Proton-Coupled O-Atom Transfer in the Oxidation of HSO₃^- by the Ruthenium Oxo Complex trans-[Ru^VI(TMC)(O)₂]²⁺ (TMC = 1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane). In: Inorganic Chemistry. 2017 ; Vol. 56, No. 21. pp. 12699-12702.