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Control of Product Distribution and Mechanism by Ligation and Electric Field in the Thermal Activation of Methane
Author(s) -
Yue Lei,
Li Jilai,
Zhou Shaodong,
Sun Xiaoyan,
Schlangen Maria,
Shaik Sason,
Schwarz Helmut
Publication year - 2017
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.201703485
Subject(s) - electric field , chemistry , chemical physics , product distribution , methane , metal , ligand (biochemistry) , hydrogen atom , hydrogen , photochemistry , thermal , bimetallic strip , catalysis , thermodynamics , physics , organic chemistry , biochemistry , receptor , alkyl , quantum mechanics
An unexpected mechanistic switch as well as a change of the product distribution in the thermal gas‐phase activation of methane have been identified when diatomic [ZnO] .+ is ligated with acetonitrile. Theoretical studies suggest that a strong metal–carbon attraction in the pristine [ZnO] .+ species plays an important role in the rebound of the incipient CH 3 . radical to the metal center, thus permitting the competitive generation of CH 3 . , OH . , and CH 3 OH. This interaction is drastically weakened by a single CH 3 CN ligand. As a result, upon ligation the proton‐coupled single electron transfer that prevails for [ZnO] .+ /CH 4 switches to the classical hydrogen‐atom‐transfer process, thus giving rise to the exclusive expulsion of CH 3 . . This ligand effect can be modeled quite well by an oriented external electric field of a negative point charge.