Gallium Hydrides with a Radical-Anionic Ligand

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

doi:10.1021/acs.inorgchem.7b02138

Gallium Hydrides with a Radical-Anionic Ligand

Inorg Chem. 2017 Nov 6;56(21):13401-13410. doi: 10.1021/acs.inorgchem.7b02138.

Authors

Vladimir G Sokolov¹, Tatyana S Koptseva¹, Mikhail V Moskalev¹, Natalia L Bazyakina¹, Alexander V Piskunov¹, Anton V Cherkasov¹, Igor L Fedushkin¹

Affiliation

¹ G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences , Tropinina 49, Nizhny Novgorod 603137, Russian Federation.

PMID: 29023115
DOI: 10.1021/acs.inorgchem.7b02138

Abstract

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-Bian^2-)Ga-Ga(dpp-Bian^2-) (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, 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.