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Gallium(I) tetrachlorogallate(III) Ga[GaCU] was prepared in quantitative yield by thermal de­composition of dichlorogallane [HGaCl 2 ] 2 , which is readily available from Et 3 SiH and [GaCl 3 ] 2 . The reaction of catechol with solutions of this gallium(I) tetrachlorogallate(III) in tetrahydrofuran leads to the evolution of hydrogen gas and affords a dinuclear gallium(III) complex with penta-coordinate metal atoms chelated and bridged by mono-deprotonated catechol ligands. In the crystalline phase tetrahydrofuran molecules are hydrogen-bonded to the hydroxy groups: [Ga(1,2 -OC 6 H 4 OH)Cl 2 (C 4 H 8 O)] 2 . The reaction with pinacol also gives hydrogen and the analogous product [Ga(OCMe 2 CMe 2 OH)Cl 2 (C 4 H 8 O)] 2 . The structures of the two compounds have been determined by X-ray diffraction. A mechanism of the new reaction has been proposed which involves oxidative addition of the diol to the solvate (THF)Cl 2 Ga-GaCl 2 (THF) present in the tetrahydrofuran solution to give a gallium hydride intermediate.

A Simple High-Yield Synthesis of Gallium(I) Tetrachlorogallate(III) and the Reaction of Digallium Tetrachloride Tetrahydrofuran Solvate with 1,2-Diols