The reaction of ClGaH with a sodium salt of the dpp-Bian radical-anion (dpp-Bian)Na (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) affords paramagnetic gallane (dpp-Bian)Ga(Cl)H (1). Oxidation of (dpp-Bian)Ga-Ga(dpp-Bian) (2) with NO results in the dimeric oxide (dpp-Bian)Ga(μ-O)Ga(dpp-Bian) (3). A treatment of the oxide 3 with phenylsilane affords paramagnetic gallium hydrides (dpp-Bian)GaH (4) and (dpp-Bian)Ga{OSi(Ph)H}H (5) depending on the reagent's stoichiometry. The reaction of digallane 2 with benzaldehyde produces pinacolate (dpp-Bian)Ga(OCHPh) (6). In the presence of PhSiH, the reaction between digallane 2 and benzaldehyde (2: PhSiH: PhC(H)O = 1:4:4) affords compound 4. The newly prepared complexes 1, 3-6 consist of a spin-labeled diimine ligand-dpp-Bian radical-anion. The presence of the ligand-localized unpaired electron allows the use of the ESR spectroscopy for characterization of the gallium hydrides reported. The molecular structures of compounds 1, 3-6 have been determined by the single-crystal X-ray analysis.
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