Sokolov Vladimir G, Koptseva Tatyana S, Moskalev Mikhail V, Bazyakina Natalia L, Piskunov Alexander V, Cherkasov Anton V, Fedushkin Igor L
G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences , Tropinina 49, Nizhny Novgorod 603137, Russian Federation.
Inorg Chem. 2017 Nov 6;56(21):13401-13410. doi: 10.1021/acs.inorgchem.7b02138.
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.
ClGaH与双二苯基膦基亚胺自由基阴离子（dpp - Bian）的钠盐（dpp - Bian = 1,2 - 双[(2,6 - 二异丙基苯基)亚氨基]苊）反应生成顺磁性镓氢化物（dpp - Bian）Ga(Cl)H（1）。用NO氧化（dpp - Bian）Ga - Ga(dpp - Bian)（2）得到二聚氧化物（dpp - Bian）Ga(μ - O)Ga(dpp - Bian)（3）。根据试剂的化学计量比，用苯基硅烷处理氧化物3可得到顺磁性镓氢化物（dpp - Bian）GaH（4）和（dpp - Bian）Ga{OSi(Ph)H}H（5）。二镓烷2与苯甲醛反应生成频哪醇（dpp - Bian）Ga(OCHPh)（6）。在PhSiH存在下，二镓烷2与苯甲醛之间的反应（2:PhSiH:PhC(H)O = 1:4:4）得到化合物4。新制备的配合物1、3 - 6由自旋标记的二亚胺配体 - dpp - Bian自由基阴离子组成。配体局部未成对电子的存在使得电子顺磁共振光谱可用于表征所报道的镓氢化物。化合物1、3 - 6的分子结构已通过单晶X射线分析确定。
