Catalytic Methane Monofunctionalization by an Electrogenerated High-Valent Pd Intermediate
| Autor: | R. Soyoung Kim, Seokjoon Oh, Yogesh Surendranath, Matthew E. O'Reilly |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2017 |
| Předmět: |
General Chemical Engineering
Sulfuric acid 02 engineering and technology General Chemistry 010402 general chemistry 021001 nanoscience & nanotechnology Photochemistry 01 natural sciences Methanesulfonic acid Redox Methane 0104 chemical sciences Catalysis lcsh:Chemistry chemistry.chemical_compound chemistry lcsh:QD1-999 Methyl bisulfate Electrophile Chemical Sciences Methanol 0210 nano-technology Research Article |
| Zdroj: | ACS Central Science, Vol 3, Iss 11, Pp 1174-1179 (2017) ACS Central Science ACS central science, vol 3, iss 11 ACS Central Science, vol 3, iss 11 |
| ISSN: | 2374-7951 2374-7943 |
| Popis: | 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 (CH3SO3H) via concurrent faradaic and nonfaradaic reaction pathways. This work enables new electrochemical approaches for promoting rapid methane monofunctionalization. Electrochemical oxidation of PdII in sulfuric acid generates a dinuclear PdIII species that rapidly converts methane to CH3OSO3H and CH3SO3H and supports continuous catalyst regeneration. |
| Databáze: | OpenAIRE |
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