Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3 −and SO3 2−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 SO₃ ²⁻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

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

5 Citations (Scopus)

Abstract

The kinetics and mechanism of the reaction of S^IV(SO₃ ²⁻+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 SO₃ ²⁻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
Journal	Chemistry - A European Journal
Volume	22
Issue number	31
Online published	23 Jun 2016
DOIs	https://doi.org/10.1002/chem.201601848
Publication status	Published - 25 Jul 2016

Research Keywords

kinetics
nitrides
reaction mechanisms
ruthenium
sulfite oxidation

Access Output

10.1002/chem.201601848

Other Access Options

Check CityUHK Library

Permanent Link

Right click to copy link

Cite this

@article{a603fe8aa44b4210ba46f200941b2a05,

title = "Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3 −and SO3 2−in Aqueous Solution",

abstract = "The kinetics and mechanism of the reaction of SIV(SO3 2−+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 SO3 2−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 Wai-Lun Man and Lam, \{William W. Y.\} and Kai-Chung Lau and Tai-Chu Lau",

year = "2016",

month = jul,

day = "25",

doi = "10.1002/chem.201601848",

language = "English",

volume = "22",

pages = "10754--10758",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley \& Sons",

number = "31",

}

TY - JOUR

T1 - Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3 −and SO3 2−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(SO3 2−+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 SO3 2−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(SO3 2−+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 SO3 2−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

UR - https://www.scopus.com/pages/publications/84977090711

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-84977090711&origin=recordpage

U2 - 10.1002/chem.201601848

DO - 10.1002/chem.201601848

M3 - RGC 21 - Publication in refereed journal

SN - 0947-6539

VL - 22

SP - 10754

EP - 10758

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 31

ER -

Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO₃ ⁻and SO₃ ²⁻in Aqueous Solution

Abstract

Research Keywords

Access Output

Other Access Options

Permanent Link

Other Files and Links

Fingerprint

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

GRF: Metal Catalyzed Oxidation of Organic Substrates by Nitrogen Oxyanions and Oxides

Cite this

Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3 −and SO3 2−in Aqueous Solution

Abstract

Research Keywords

Access Output

Other Access Options

Permanent Link

Other Files and Links

Fingerprint

Projects

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

GRF: Metal Catalyzed Oxidation of Organic Substrates by Nitrogen Oxyanions and Oxides

Cite this

Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO₃ ⁻and SO₃ ²⁻in Aqueous Solution