Simultaneous Formation of cis- and trans-CH3OCu(OH) Intermediates in Methane Activation by Cu in Solid Ar

Autor:	Yanying Zhao, Zhaoman Zhou, Fan Yu, Caixia Wang
Rok vydání:	2019
Předmět:	Matrix isolation Infrared spectroscopy chemistry.chemical_element Reaction intermediate Photochemistry Copper Methane Transition state Catalysis Inorganic Chemistry chemistry.chemical_compound chemistry Physical and Theoretical Chemistry Cis–trans isomerism
Zdroj:	Inorganic Chemistry. 58:3237-3246
ISSN:	1520-510X 0020-1669
DOI:	10.1021/acs.inorgchem.8b03322
Popis:	Understanding the mechanisms of methane activation is an important and active research area of the contemporary catalyzed conversion of hydrocarbons to shippable, valuable feedstock and has invoked close collaborations between experimentalists and theorists. This article describes the trapping of reaction intermediates in a copper-catalyzed direct methane-to-methanol conversion. Specifically, two hydroxy(methoxy)copper(I) [CH3OCu(OH)] isomeric intermediates were distinguished and characterized by matrix isolation infrared spectroscopy and 18O2, CD4, and 13CH4 isotopic substitution experiments combined with quantum chemical calculations. Initially, laser-evaporated copper reacted with oxygen to form CuO2. Upon successive broadband UV irradiation, methane activation via the insertion of CuO2 into one of the C–H bonds produced both cis- and trans-CH3OCu(OH). All possible structures of the reactants, intermediates, transition states, minimum-energy crossing points, and products were optimized. The results ind...
Databáze:	OpenAIRE
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