Chuan-Pin Chen,Oluwafemi Abubakar,Xiaoyin Zhang,Thomas W Hamann
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Electrocatalytic Ammonia Oxidation with Coordinatively Saturated Ruthenium Catalyst.
This communication describes the investigation of a coordinatively saturated complex [Ru(tpy)(dmabpy)Cl]+ ([Ru(Cl)]+) as an ammonia oxidation catalyst. Cyclic voltammetry measurements show an ideal S-shaped wave, indicating total catalysis conditions with a kobs (TOFmax) of 9360 h-1. The reaction was found to be first-order in [Ru(Cl)]+ and third-order in [NH3]. Stoichiometric reactions of the one-electron oxidized species, [Ru(Cl)]2+, were monitored following the addition of 15NH3 using 1H and 15N NMR spectroscopy. These experiments showed that the chloride-coordinated complex rapidly converts NH3 to N2. NMR spectroscopy and electrochemistry results definitively show that NH3 does not substitute the Cl- ligand to form the previously reported [Ru(NH3)]2+ catalyst which operates by a different mechanistic pathway. Taken together these results indicate outersphere electron transfer mediated ammonia oxidation reaction.
期刊介绍:
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.