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

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)

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

^*Corresponding author for this work

Department of Chemistry

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

5 Citations (Scopus)

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.

Original language	English
Pages (from-to)	12699-12702
Journal	Inorganic Chemistry
Volume	56
Issue number	21
Online published	13 Oct 2017
DOIs	https://doi.org/10.1021/acs.inorgchem.7b02509
Publication status	Published - 6 Nov 2017

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@article{f32e575c32c04859b56932e737c1764d,

title = "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)",

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.",

author = "Qian Wang and Zhao, \{Hong Yan\} and Po-Kam Lo and Lam, \{William W. Y.\} and Kai-Chung Lau and Tai-Chu Lau",

year = "2017",

month = nov,

day = "6",

doi = "10.1021/acs.inorgchem.7b02509",

language = "English",

volume = "56",

pages = "12699--12702",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "21",

}

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

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - 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)

AU - Wang, Qian

AU - Zhao, Hong Yan

AU - Lo, Po-Kam

AU - Lam, William W. Y.

AU - Lau, Kai-Chung

AU - Lau, Tai-Chu

PY - 2017/11/6

Y1 - 2017/11/6

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/85033403368

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U2 - 10.1021/acs.inorgchem.7b02509

DO - 10.1021/acs.inorgchem.7b02509

M3 - RGC 21 - Publication in refereed journal

SN - 0020-1669

VL - 56

SP - 12699

EP - 12702

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 21

ER -

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)

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GRF: Theoretical Studies of Oxidation of Organic Compounds by Ferrate(VI) and Ferrate(V)

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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)

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GRF: Theoretical Studies of Oxidation of Organic Compounds by Ferrate(VI) and Ferrate(V)

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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)