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Selective Activation of Methyl C–H Bonds of Toluene by Oxygen on Metallic Gold

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Abstract

In accord with its gas phase acidity, toluene is activated by atomic oxygen adsorbed on Au(111) at the methyl C–H bonds. Titration of this species from the surface with HCOOD yields C6H5CHD2, indicating that much of the toluene has been doubly deprotonated at the methyl carbon. Even at low surface coverages of atomic oxygen the thusly-activated species yields only CO, CO2 and water as gas phase products when heated above room temperature, indicating the facile formation of an adsorbed benzoate, not simple oxygen insertion into the carbene to form benzyl benzyloxy. At higher O pre-coverages benzoic acid forms between 400 and 500 K.

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Acknowledgements

R.J.M and J.C.F.R.-R. gratefully acknowledge the support of the National Science Foundation for this research (NSF CHE 0952790). C.M.F gratefully acknowledges support of the U.S. Department of Energy, Basic Energy Sciences, Grant No. FG02-84-ER13289. This work was partially supported as part of the Integrated Mesoscale Architectures for Sustainable Catalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Grant No. DE-SC0012573.

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Correspondence to Robert J. Madix.

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Rodríguez-Reyes, J.C.F., Friend, C.M. & Madix, R.J. Selective Activation of Methyl C–H Bonds of Toluene by Oxygen on Metallic Gold. Catal Lett 148, 1985–1989 (2018). https://doi.org/10.1007/s10562-018-2407-3

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  • DOI: https://doi.org/10.1007/s10562-018-2407-3

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