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Stable Radical Cation and Dication of an N‐Heterocyclic Carbene Stabilized Digallene: Synthesis, Characterization and Reactivity
Author(s) -
Feng Zhongtao,
Fang Yong,
Ruan Huapeng,
Zhao Yue,
Tan Gengwen,
Wang Xinping
Publication year - 2020
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.202000051
Subject(s) - dication , chemistry , carbene , reactivity (psychology) , radical ion , electron paramagnetic resonance , gallium , photochemistry , hydride , sulfide , double bond , crystallography , medicinal chemistry , ion , polymer chemistry , organic chemistry , metal , medicine , physics , alternative medicine , pathology , nuclear magnetic resonance , catalysis
One‐ and two‐electron oxidation of a digallene stabilized by an N‐heterocyclic carbene afforded the first stable gallium‐based radical cation and dication salts, respectively. Structural analysis and theoretical calculations reveal that the oxidation occurs at the Ga=Ga double bond, leading to removal of π electrons of the double bond and a decrease of the bond order. The spin density of the radical cation mainly locates at the two gallium centers as demonstrated by EPR spectroscopy and theoretical calculations. Moreover, the reactivity of the radical cation salt toward n Bu 3 SnH and cyclo‐S 8 was studied; a digallium–hydride cation salt containing a Ga−Ga single bond and a gallium sulfide cluster bearing an unprecedented ladder‐like Ga 4 S 4 core structure were obtained, respectively.