Journal of the American Chemical Society
Communication
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methanol is also notable. Oxidative activation of nanoITO-
RuII(OH2)2+ in acidic solution provides access to nanoITO-
RuIV(OH)3+ (pKa ∼3). It was previously shown that nanoITO-
RuIV(OH)3+ is an electrocatalyst for oxidation of benzyl
alcohol.8f At 1.3 V, -RuIV(OH)3+ selectively oxidizes MTO to
methanol in 87% Faradaic yield. Selectivity is lost at 1.4 and 1.5
V due to overoxidation of MTO by -RuV(O)3+. The available
kinetic and mechanistic information points to a mechanism
involving -RuIV(OH)3+ insertion into the Re−C bond of MTO.
The reaction proceeds through a detectable intermediate which,
at high MTO concentrations, accumulates on the surface
undergoing hydrolysis to methanol and perrhenate.
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ASSOCIATED CONTENT
* Supporting Information
■
S
Experimental methods, CV and chronoamperometric data, and
spectroelectrochemical data are provided. This material is
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AUTHOR INFORMATION
Corresponding Author
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́
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Funding by the Center for Catalytic Hydrocarbon Function-
alization, an Energy Frontier Research Center (EFRC), funded
by the U.S. Department of Energy (DOE), Office of Science,
Office of Basic Energy Sciences, under Award DE-SC0001298
is gratefully acknowledged for supporting M.K.C. and M.A.M.
Funding by the UNC EFRC Center for Solar Fuels, an EFRC
funded by the U.S. DOE, Office of Science, Office of Basic
Energy Sciences, under Award DE-SC0001011 is gratefully
acknowledged for supporting J.J.C.
(7) Pouy, M. J.; Milczek, E. M.; Figg, T. M.; Otten, B. M.; Prince, B.
M.; Gunnoe, T. B.; Cundari, T. R.; Groves, J. T. J. Am. Chem. Soc.
2012, 134, 12920−12923.
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