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Ag II ‐Mediated Electrocatalytic Ambient CH 4 Functionalization Inspired by HSAB Theory
Author(s) -
Xiang Danlei,
Iñiguez Jesus A.,
Deng Jiao,
Guan Xun,
Martinez Antonio,
Liu Chong
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202104217
Subject(s) - chemistry , activation energy , hsab theory , reaction rate constant , transition metal , ambient pressure , reactivity (psychology) , inorganic chemistry , kinetics , catalysis , organic chemistry , thermodynamics , medicine , physics , alternative medicine , pathology , quantum mechanics
Although most class (b) transition metals have been studied in regard to CH 4 activation, divalent silver (Ag II ), possibly owing to its reactive nature, is the only class (b) high‐valent transition metal center that is not yet reported to exhibit reactivities towards CH 4 activation. We now report that electrochemically generated Ag II metalloradical readily functionalizes CH 4 into methyl bisulfate (CH 3 OSO 3 H) at ambient conditions in 98 % H 2 SO 4 . Mechanistic investigation experimentally unveils a low activation energy of 13.1 kcal mol −1 , a high pseudo‐first‐order rate constant of CH 4 activation up to 2.8×10 3 h −1 at room temperature and a CH 4 pressure of 85 psi, and two competing reaction pathways preferable towards CH 4 activation over solvent oxidation. Reaction kinetic data suggest a Faradaic efficiency exceeding 99 % beyond 180 psi CH 4 at room temperature for potential chemical production from widely distributed natural gas resources with minimal infrastructure reliance.