Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3and 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

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

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 HSO3and SO32−by RuVIN. A deuterium isotope effect of 4.7 is observed in the HSO3pathway. Based on experimental results and DFT calculations the proposed mechanism involves concerted N−S bond formation (partial N-atom transfer) between RuVIN and HSO3and H+transfer from HSO3to a H2O molecule.

Original languageEnglish
Pages (from-to)10754-10758
Number of pages5
JournalChemistry - A European Journal
Volume22
Issue number31
Early online date1 Jun 2016
DOIs
Publication statusPublished - 25 Jul 2016

Scopus Subject Areas

  • Catalysis
  • Organic Chemistry

User-Defined Keywords

  • kinetics
  • nitrides
  • reaction mechanisms
  • ruthenium
  • sulfite oxidation

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