The reduction of metal nitride to ammonia is a key step in biological and chemical nitrogen fixation. We report herein the facile reduction of a ruthenium(VI) nitrido complex [(L)Ru(N)(OH)] (1, L = N, N'-bis(salicylidene)- o-cyclohexyldiamine dianion) to [(L)Ru(NH)(OH)] by l-cysteine (Cys), an ubiquitous biological reductant, in aqueous solution. At pH 1.0-5.3, the reaction has the following stoichiometry: [(L)Ru(N)(OH)] + 3HSCHCH(NH)CO → [(L)Ru(NH)(OH)] + 1.5(SCHCH(NH)CO). Kinetic studies show that at pH 1 the reaction consists of two phases, while at pH 5 there are three distinct phases. For all phases the rate law is rate = k[1][Cys]. Studies on the effects of acidity indicate that both HSCHCH(NH)CO and SCHCH(NH)CO are kinetically active species. At pH 1, the reaction is proposed to go through [(L)Ru(NHSCHCHNHCOH)(OH)] (2a), [(L)Ru(NHSCHCHNHCOH)(OH)] (3), and [(L)Ru(NH)(OH)] (4) intermediates. On the other hand, at pH around 5, the proposed intermediates are [(L)Ru(NHSCHCHNHCO)(OH)] (2b) and [(L)Ru(NH)(OH)] (4). The intermediate ruthenium(IV) sulfilamido species, [(L)Ru(NHSCHCHNHCOH)(OH)] (2a) and the final ruthenium(III) ammine species, [(L)Ru(NH)(MeOH)] (5) (where HO was replaced by MeOH) have been isolated and characterized by various spectroscopic methods.
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