Electrooxidation of Alcohols Catalyzed by Amino Alcohol Ligated Ruthenium Complexes

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• 作者：Kristen R. Brownell ; Charles C. L. McCrory ; Christopher E. D. Chidsey ; Richard H. Perry ; Richard N. Zare ; Robert M. Waymouth
• 刊名：Journal of the American Chemical Society
• 出版年：2013
• 出版时间：September 25, 2013
• 年：2013
• 卷：135
• 期：38
• 页码：14299-14305
• 全文大小：384K
• 年卷期：v.135,no.38(September 25, 2013)
• ISSN：1520-5126

文摘

Ruthenium transfer hydrogenation catalysts physisorbed onto edge-plane graphite electrodes are active electrocatalysts for the oxidation of alcohols. Electrooxidation of CH₃OH (1.23 M) in a buffered aqueous solution at pH 11.5 with [(畏⁶-p-cymene)(畏²-N,O-(1R,2S)-cis-1-amino-2-indanol)]Ru^IICl (2) on edge-plane graphite exhibits an onset current at 560 mV vs NHE. Koutecky鈥揕evich analysis at 750 mV reveals a four-electron oxidation of methanol with a rate of 1.35 M^鈥? s^鈥?. Mechanistic investigations by ¹H NMR, cyclic voltammetry, and desorption electrospray ionization mass spectrometry indicate that the electroxidation of methanol to generate formate is mediated by surface-supported Ru鈥搊xo complexes.