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A Homoleptic Ga4 Radical Anion: Isolation, Characterization, and Reactivity
Lijie Pei1, Yushuang Zhang2, Cong Fan1
1College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, Hangzhou, China.
None:
We report the synthesis and characterization of a homoleptic Ga4 radical anion ([Li+]•[1•-]), prepared via a salt-metathesis reaction between Cp*Ga (Cp* = pentamethylcyclopentadienyl) and [Li2(L)] (L = Me2Si(DipN)2). Combined structural and computational analyses reveal a nearly planar geometry at the central gallium atom, with only minimal distortion toward a trigonal pyramidal geometry, and the unpaired spin density localized in its 4p orbital. Density functional theory (DFT) calculations elucidate the reaction mechanism for the formation of [Li+]•[1•-], while N-heterocyclic carbene (NHC)-trapping experiments led to the isolation of NHC-stabilized digallyl digallenes (2a and 2b) as well as a digallyl-substituted gallium radical (3c). Compound [Li+]•[1•-] exhibits versatile gallium-centered radical reactivity, including one-electron oxidation with S8 and facile E─E bond activation (E = S, Se, and I) toward PhS-SPh, PhSe-SePh, and I2.
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