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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.