Electrooxidation of alcohols catalyzed by amino alcohol ligated ruthenium complexes

Kristen R. Brownell; Charles C.L. Mccrory; Christopher E.D. Chidsey; Richard H. Perry; Richard N. Zare; Robert M. Waymouth

doi:10.1021/ja4055564

Electrooxidation of alcohols catalyzed by amino alcohol ligated ruthenium complexes

Kristen R. Brownell, Charles C.L. Mccrory, Christopher E.D. Chidsey, Richard H. Perry, Richard N. Zare, Robert M. Waymouth

Research output: Contribution to journal › Article › peer-review

Abstract

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 [(η⁶-p-cymene)(η²-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-Levich analysis at 750 mV reveals a four-electron oxidation of methanol with a rate of 1.35 M^-1 s ^-1. 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-oxo complexes.

Original language	English (US)
Pages (from-to)	14299-14305
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	135
Issue number	38
DOIs	https://doi.org/10.1021/ja4055564
State	Published - Sep 25 2013
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja4055564

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title = "Electrooxidation of alcohols catalyzed by amino alcohol ligated ruthenium complexes",

abstract = "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 [(η6-p-cymene)(η2-N,O-(1R,2S)-cis-1- amino-2-indanol)]RuIICl (2) on edge-plane graphite exhibits an onset current at 560 mV vs NHE. Koutecky-Levich analysis at 750 mV reveals a four-electron oxidation of methanol with a rate of 1.35 M-1 s -1. 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-oxo complexes.",

author = "Brownell, {Kristen R.} and Mccrory, {Charles C.L.} and Chidsey, {Christopher E.D.} and Perry, {Richard H.} and Zare, {Richard N.} and Waymouth, {Robert M.}",

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doi = "10.1021/ja4055564",

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volume = "135",

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T1 - Electrooxidation of alcohols catalyzed by amino alcohol ligated ruthenium complexes

AU - Brownell, Kristen R.

AU - Mccrory, Charles C.L.

AU - Chidsey, Christopher E.D.

AU - Perry, Richard H.

AU - Zare, Richard N.

AU - Waymouth, Robert M.

PY - 2013/9/25

Y1 - 2013/9/25

N2 - 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 [(η6-p-cymene)(η2-N,O-(1R,2S)-cis-1- amino-2-indanol)]RuIICl (2) on edge-plane graphite exhibits an onset current at 560 mV vs NHE. Koutecky-Levich analysis at 750 mV reveals a four-electron oxidation of methanol with a rate of 1.35 M-1 s -1. 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-oxo complexes.

AB - 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 [(η6-p-cymene)(η2-N,O-(1R,2S)-cis-1- amino-2-indanol)]RuIICl (2) on edge-plane graphite exhibits an onset current at 560 mV vs NHE. Koutecky-Levich analysis at 750 mV reveals a four-electron oxidation of methanol with a rate of 1.35 M-1 s -1. 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-oxo complexes.

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Electrooxidation of alcohols catalyzed by amino alcohol ligated ruthenium complexes

Abstract

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