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On the Mechanisms of Hydrogen‐Atom Transfer from Water to the Heteronuclear Oxide Cluster [Ga 2 Mg 2 O 5 ] .+ : Remarkable Electronic Structure Effects
Author(s) -
Li Jilai,
Zhou Shaodong,
Wu XiaoNan,
Tang Shiya,
Schlangen Maria,
Schwarz Helmut
Publication year - 2015
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.201505336
Subject(s) - heteronuclear molecule , chemistry , lone pair , hydrogen atom , proton coupled electron transfer , electron transfer , proton , intramolecular force , cluster (spacecraft) , crystallography , chemical physics , atomic physics , photochemistry , stereochemistry , molecule , nuclear magnetic resonance spectroscopy , physics , alkyl , organic chemistry , quantum mechanics , computer science , programming language
Mechanistic insight into the homolytic cleavage of the OH bond of water by the heteronuclear oxide cluster [Ga 2 Mg 2 O 5 ] .+ has been derived from state‐of‐the‐art gas‐phase experiments in conjunction with quantum chemical calculations. Three pathways have been identified computationally. In addition to the conventional hydrogen‐atom transfer (HAT) to the radical center of a bridging oxygen atom, two mechanistically distinct proton‐coupled electron‐transfer (PCET) processes have been identified. The energetically most favored path involves initial coordination of the incoming water ligand to a magnesium atom followed by an intramolecular proton transfer to the lone‐pair of the bridging oxygen atom. This step, which is accomplished by an electronic reorganization, generates two structurally equivalent OH groups either of which can be liberated, in agreement with labeling experiments.