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The Electric Field as a “Smart” Ligand in Controlling the Thermal Activation of Methane and Molecular Hydrogen
Author(s) -
Yue Lei,
Wang Na,
Zhou Shaodong,
Sun Xiaoyan,
Schlangen Maria,
Schwarz Helmut
Publication year - 2018
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.201805718
Subject(s) - ligand (biochemistry) , electric field , chemistry , methane , hydrogen , oxide , hydrogen bond , molecule , organic chemistry , physics , biochemistry , receptor , quantum mechanics
While pristine [TaO 2 ] + is rather inert in its thermal reactions with both methane and molecular hydrogen, the cluster oxide becomes reactive upon ligation with the closed‐shell ligand CO 2 . While the presence of CO 2 increases the intrinsic barriers of the C−H and H−H bond activation steps, the efficiency of the overall reaction to generate the insertion product [Ta(R)(OH)O] + (R=CH 3 , H) is greatly enhanced by the superb leaving‐group properties of CO 2 . The ligand effect of CO 2 has been well mimicked by the electric field of a negative point charge, and mechanistic aspects are addressed by high‐level quantum chemical calculations