Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3−and SO32−in Aqueous Solution

Qian Wang; Hong Yan Zhao; Wai Lun Man; William W.Y. Lam; Kai Chung Lau; Tai Chu Lau

doi:10.1002/chem.201601848

Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO₃⁻and SO₃²⁻in Aqueous Solution

Qian Wang, Hong Yan Zhao, Wai Lun Man, William W.Y. Lam, Kai Chung Lau^*, Tai Chu Lau^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal article › peer-review

4 Citations (Scopus)

Abstract

The kinetics and mechanism of the reaction of S^IV(SO₃²⁻+HSO₃⁻) with a ruthenium(VI) nitrido complex, [(L)Ru^VI(N)(OH₂)]⁺(Ru^VIN, L=N,N′-bis(salicylidene)-o-cyclohexyldiamine dianion), in aqueous acidic solutions are reported. The kinetic results are consistent with parallel pathways involving oxidation of HSO₃⁻and SO₃²⁻by Ru^VIN. A deuterium isotope effect of 4.7 is observed in the HSO₃⁻pathway. Based on experimental results and DFT calculations the proposed mechanism involves concerted N−S bond formation (partial N-atom transfer) between Ru^VIN and HSO₃⁻and H⁺transfer from HSO₃⁻to a H₂O molecule.

Original language	English
Pages (from-to)	10754-10758
Number of pages	5
Journal	Chemistry - A European Journal
Volume	22
Issue number	31
Early online date	1 Jun 2016
DOIs	https://doi.org/10.1002/chem.201601848
Publication status	Published - 25 Jul 2016

Scopus Subject Areas

Catalysis
Organic Chemistry

User-Defined Keywords

kinetics
nitrides
reaction mechanisms
ruthenium
sulfite oxidation

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10.1002/chem.201601848

Cite this

@article{1464edf9fed84411a572ffa2a1e427ab,

title = "Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3−and SO32−in Aqueous Solution",

abstract = "The kinetics and mechanism of the reaction of SIV(SO32−+HSO3−) with a ruthenium(VI) nitrido complex, [(L)RuVI(N)(OH2)]+(RuVIN, L=N,N′-bis(salicylidene)-o-cyclohexyldiamine dianion), in aqueous acidic solutions are reported. The kinetic results are consistent with parallel pathways involving oxidation of HSO3−and SO32−by RuVIN. A deuterium isotope effect of 4.7 is observed in the HSO3−pathway. Based on experimental results and DFT calculations the proposed mechanism involves concerted N−S bond formation (partial N-atom transfer) between RuVIN and HSO3−and H+transfer from HSO3−to a H2O molecule.",

keywords = "kinetics, nitrides, reaction mechanisms, ruthenium, sulfite oxidation",

author = "Qian Wang and Zhao, {Hong Yan} and Man, {Wai Lun} and Lam, {William W.Y.} and Lau, {Kai Chung} and Lau, {Tai Chu}",

note = "Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2016",

month = jul,

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doi = "10.1002/chem.201601848",

language = "English",

volume = "22",

pages = "10754--10758",

journal = "Chemistry - A European Journal",

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TY - JOUR

T1 - Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3−and SO32−in Aqueous Solution

AU - Wang, Qian

AU - Zhao, Hong Yan

AU - Man, Wai Lun

AU - Lam, William W.Y.

AU - Lau, Kai Chung

AU - Lau, Tai Chu

PY - 2016/7/25

Y1 - 2016/7/25

N2 - The kinetics and mechanism of the reaction of SIV(SO32−+HSO3−) with a ruthenium(VI) nitrido complex, [(L)RuVI(N)(OH2)]+(RuVIN, L=N,N′-bis(salicylidene)-o-cyclohexyldiamine dianion), in aqueous acidic solutions are reported. The kinetic results are consistent with parallel pathways involving oxidation of HSO3−and SO32−by RuVIN. A deuterium isotope effect of 4.7 is observed in the HSO3−pathway. Based on experimental results and DFT calculations the proposed mechanism involves concerted N−S bond formation (partial N-atom transfer) between RuVIN and HSO3−and H+transfer from HSO3−to a H2O molecule.

AB - The kinetics and mechanism of the reaction of SIV(SO32−+HSO3−) with a ruthenium(VI) nitrido complex, [(L)RuVI(N)(OH2)]+(RuVIN, L=N,N′-bis(salicylidene)-o-cyclohexyldiamine dianion), in aqueous acidic solutions are reported. The kinetic results are consistent with parallel pathways involving oxidation of HSO3−and SO32−by RuVIN. A deuterium isotope effect of 4.7 is observed in the HSO3−pathway. Based on experimental results and DFT calculations the proposed mechanism involves concerted N−S bond formation (partial N-atom transfer) between RuVIN and HSO3−and H+transfer from HSO3−to a H2O molecule.

KW - kinetics

KW - nitrides

KW - reaction mechanisms

KW - ruthenium

KW - sulfite oxidation

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DO - 10.1002/chem.201601848

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JO - Chemistry - A European Journal

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