Catalytic Methane Monofunctionalization by an Electrogenerated High-Valent Pd Intermediate
Author(s)
O'Reilly, Matthew E; Kim, R. Soyoung; Oh, Seokjoon; Surendranath, Yogesh
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Electrophilic high-valent metal ions are potent intermediates for the catalytic functionalization of methane, but in many cases, their high redox potentials make these intermediates difficult or impossible to access using mild stoichiometric oxidants derived from O₂. Herein, we establish electrochemical oxidation as a versatile new strategy for accessing high-valent methane monofunctionalization catalysts. We provide evidence for the electrochemical oxidation of simple PdSO₄ in concentrated sulfuric acid electrolytes to generate a putative Pd₂III,III species in an all-oxidic ligand field. This electrogenerated high-valent Pd complex rapidly activates methane with a low barrier of 25.9 (±2.6) kcal/mol, generating methanol precursors methyl bisulfate (CH₃OSO₃H) and methanesulfonic acid (CH₃SO ₃H) via concurrent faradaic and nonfaradaic reaction pathways. This work enables new electrochemical approaches for promoting rapid methane monofunctionalization.
Date issued
2017-11Department
Massachusetts Institute of Technology. Department of Chemistry; Koch Institute for Integrative Cancer Research at MITJournal
ACS Central Science
Publisher
American Chemical Society (ACS)
Citation
O’Reilly, Matthew E. et al. “Catalytic Methane Monofunctionalization by an Electrogenerated High-Valent Pd Intermediate.” ACS Central Science 3, 11 (October 2017): 1174–1179 © 2017 American Chemical Society
Version: Final published version
ISSN
2374-7943
2374-7951