TY - JOUR
T1 - Control of Product Distribution and Mechanism by Ligation and Electric Field in the Thermal Activation of Methane
AU - Yue, Lei
AU - Li, Jilai
AU - Zhou, Shaodong
AU - Sun, Xiaoyan
AU - Schlangen, Maria
AU - Shaik, Sason
AU - Schwarz, Helmut
N1 - Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/8/14
Y1 - 2017/8/14
N2 - 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 CH3. radical to the metal center, thus permitting the competitive generation of CH3., OH., and CH3OH. This interaction is drastically weakened by a single CH3CN ligand. As a result, upon ligation the proton-coupled single electron transfer that prevails for [ZnO].+/CH4 switches to the classical hydrogen-atom-transfer process, thus giving rise to the exclusive expulsion of CH3.. This ligand effect can be modeled quite well by an oriented external electric field of a negative point charge.
AB - 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 CH3. radical to the metal center, thus permitting the competitive generation of CH3., OH., and CH3OH. This interaction is drastically weakened by a single CH3CN ligand. As a result, upon ligation the proton-coupled single electron transfer that prevails for [ZnO].+/CH4 switches to the classical hydrogen-atom-transfer process, thus giving rise to the exclusive expulsion of CH3.. This ligand effect can be modeled quite well by an oriented external electric field of a negative point charge.
KW - external electric field
KW - gas-phase reaction
KW - hydrogen-atom transfer
KW - ligand effect
KW - methane activation
UR - http://www.scopus.com/inward/record.url?scp=85019633125&partnerID=8YFLogxK
U2 - 10.1002/anie.201703485
DO - 10.1002/anie.201703485
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C2 - 28544127
AN - SCOPUS:85019633125
SN - 1433-7851
VL - 56
SP - 10219
EP - 10223
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 34
ER -