Journal
ACS CENTRAL SCIENCE
Volume 3, Issue 11, Pages 1174-1179Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscentsci.7b00342
Keywords
-
Categories
Funding
- Eni S.p.A. through MIT Energy Initiative
- MIT Department of Chemistry
Ask authors/readers for more resources
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 O-2. 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 Pd-2 (III),(III) species in an all-oxidic ligand field. This electro-generated 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 (CH3SO3H) via concurrent faradaic and nonfaradaic reaction pathways. This work enables new electrochemical approaches for promoting rapid methane monofunctionalization.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available