Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO 3  −  and SO 3  2−  in Aqueous Solution | Zendy

Wang Qian | Zendy; Zhao Hong Yan | Zendy; Man WaiLun | Zendy; Lam William W. Y. | Zendy; Lau KaiChung | Zendy; Lau TaiChu | Zendy

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Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO 3 − and SO 3 2− in Aqueous Solution

Author(s) -

Wang Qian,

Zhao Hong Yan,

Man WaiLun,

Lam William W. Y.,

Lau KaiChung,

Lau TaiChu

Publication year - 2016

Publication title -

chemistry – a european journal

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.687

H-Index - 242

eISSN - 1521-3765

pISSN - 0947-6539

DOI - 10.1002/chem.201601848

Subject(s) - ruthenium , chemistry , kinetic isotope effect , kinetics , aqueous solution , deuterium , reaction mechanism , chemical kinetics , molecule , atom (system on chip) , catalysis , organic chemistry , physics , quantum mechanics , computer science , embedded system

The kinetics and mechanism of the reaction of S IV (SO 3 2− +HSO 3 − ) with a ruthenium(VI) nitrido complex, [(L)Ru VI (N)(OH 2 )] + (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 HSO 3 − and SO 3 2− by Ru VI N. A deuterium isotope effect of 4.7 is observed in the HSO 3 − 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 HSO 3 − and H + transfer from HSO 3 − to a H 2 O molecule.

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