Water Oxidation Intermediates Applied to Catalysis: Benzyl Alcohol Oxidation
- 6 February 2012
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 134 (9), 3972-3975
- https://doi.org/10.1021/ja210718u
Abstract
Four distinct intermediates, RuIV═O2+, RuIV(OH)3+, RuV═O3+, and RuV(OO)3+, formed by oxidation of the catalyst [Ru(Mebimpy)(4,4′-((HO)2OPCH2)2bpy)(OH2)]2+ [Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl) and 4,4′-((HO)2OPCH2)2bpy = 4,4′-bismethylenephosphonato-2,2′-bipyridine] on nanoITO (1-PO3H2) have been identified and utilized for electrocatalytic benzyl alcohol oxidation. Significant catalytic rate enhancements are observed for RuV(OO)3+ (∼3000) and RuIV(OH)3+ (∼2000) compared to RuIV═O2+. The appearance of an intermediate for RuIV═O2+ as the oxidant supports an O-atom insertion mechanism, and H/D kinetic isotope effects support net hydride-transfer oxidations for RuIV(OH)3+ and RuV(OO)3+. These results illustrate the importance of multiple reactive intermediates under catalytic water oxidation conditions and possible control of electrocatalytic reactivity on modified electrode surfaces.This publication has 15 references indexed in Scilit:
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