Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3− and SO32− in Aqueous Solution |
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| Authors: | Dr Qian Wang Hong Yan Zhao Dr Wai‐Lun Man Dr William W Y Lam Dr Kai‐Chung Lau Prof Tai‐Chu Lau |
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| Institution: | Department of Biology and Chemistry and Institute of Molecular Functional Materials, City University of Hong Kong, Hong Kong, China |
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| 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 HSO3? and SO32? 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. |
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| Keywords: | kinetics nitrides reaction mechanisms ruthenium sulfite oxidation |
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