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Gallium Hydrides with a Radical-Anionic Ligand

Posted on 2017-10-12 - 14:22
The reaction of Cl2GaH 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-Bian2–)­Ga–Ga­(dpp-Bian2–) (2) with N2O results in the dimeric oxide (dpp-Bian•–)­Ga­(μ2-O)2Ga­(dpp-Bian•–) (3). A treatment of the oxide 3 with phenylsilane affords paramagnetic gallium hydrides (dpp-Bian•–)­GaH2 (4) and (dpp-Bian•–)­Ga­{OSi­(Ph)­H2}H (5) depending on the reagent’s stoichiometry. The reaction of digallane 2 with benzaldehyde produces pinacolate (dpp-Bian•–)­Ga­(O2C2H2Ph2) (6). In the presence of PhSiH3, the reaction between digallane 2 and benzaldehyde (2: PhSiH3: PhC­(H)­O = 1:4:4) affords compound 4. The newly prepared complexes 1, 36 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, 36 have been determined by the single-crystal X-ray analysis.

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Inorganic Chemistry

AUTHORS (7)

Vladimir G. Sokolov
Tatyana S. Koptseva
Mikhail V. Moskalev
Natalia L. Bazyakina
Alexander V. Piskunov
Anton V. Cherkasov
Igor L. Fedushkin
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