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 S(IV) (SO3 (2-) +HSO3 (-) ) with a ruthenium(VI) nitrido complex, [(L)Ru(VI) (N)(OH2 )](+) (Ru(VI) N, 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(VI) N. 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(VI) N and HSO3 (-) and H(+) transfer from HSO3 (-) to a H2 O molecule.
authors.affiliation: Department of Biology and Chemistry and Institute of Molecular Functional Materials, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, China.
authors.forename: Qian
authors.initials: Q
authors.lastname: Wang
authors.affiliation: Department of Biology and Chemistry and Institute of Molecular Functional Materials, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, China.
authors.forename: Hong Yan
authors.initials: HY
authors.lastname: Zhao
authors.affiliation: Department of Biology and Chemistry and Institute of Molecular Functional Materials, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, China.
authors.forename: Wai-Lun
authors.initials: WL
authors.lastname: Man
authors.affiliation: Department of Biology and Chemistry and Institute of Molecular Functional Materials, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, China.
authors.forename: William W Y
authors.initials: WW
authors.lastname: Lam
authors.affiliation: Department of Biology and Chemistry and Institute of Molecular Functional Materials, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, China. kaichung@cityu.edu.hk.
authors.forename: Kai-Chung
authors.initials: KC
authors.lastname: Lau
authors.affiliation: Department of Biology and Chemistry and Institute of Molecular Functional Materials, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, China. bhtclau@cityu.edu.hk.
authors.forename: Tai-Chu
authors.initials: TC
authors.lastname: Lau
keywords: kinetics; nitrides; reaction mechanisms; ruthenium; sulfite oxidation