The reduction of digallane [(dpp-bian)Ga-Ga(dpp-bian)] (1) (dpp-bian=1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with lithium and sodium in diethyl ether, or with potassium in THF affords compounds featuring the direct alkali metal-gallium bonds, [(dpp-bian)Ga-Li(Et(2)O)(3)] (2), [(dpp-bian)Ga-Na(Et(2)O)(3)] (3), and [(dpp-bian)Ga-K(thf)(5)] (7), respectively. Crystallization of 3 from DME produces compound [(dpp-bian)Ga-Na(dme)(2)] (4). Dissolution of 3 in THF and subsequent crystallization from diethyl ether gives [(dpp-bian)Ga-Na(thf)(3)(Et(2)O)] (5). Ionic [(dpp-bian)Ga](-)[Na([18]crown-6)(thf)(2)](+) (6a) and [(dpp-bian)Ga](-)[Na(Ph(3)PO)(3)(thf)](+) (6b) were obtained from THF after treatment of 3 with [18]crown-6 and Ph(3)PO, respectively. The reduction of 1 with Group 2 metals in THF affords [(dpp-bian)Ga](2)M(thf)(n) (M=Mg (8), n=3; M=Ca (9), Sr (10), n=4; M=Ba (11), n=5). The molecular structures of 4-7 and 11 have been determined by X-ray crystallography. The Ga-Na bond lengths in 3-5 vary notably depending on the coordination environment of the sodium atom.
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The reaction of digallane (dpp-bian)Ga-Ga(dpp-bian) (2) (dpp-bian=1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with allyl chloride (AllCl) proceeded by a two-electron oxidative addition to afford paramagnetic complexes (dpp-bian)Ga(η -All)Cl (3) and (dpp-bian)(Cl)Ga-Ga(Cl)(dpp-bian) (4). Treatment of complex 4 with pyridine induced an intramolecular redox process, which resulted in the diamagnetic complex (dpp-bian)Ga(Py)Cl (5). In reaction with allyl bromide, complex 2 gave metal- and ligand-centered addition products (dpp-bian)Ga(η -All)Br (6) and (dpp-bian-All)(Br)Ga-Ga(Br)(dpp-bian-All) (7).
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G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences , Tropinina 49, Nizhny Novgorod 603137, Russian Federation.
The reactivity of digallane (dpp-Bian)Ga-Ga(dpp-Bian) (1) (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) toward acenaphthenequinone (AcQ), sulfur dioxide, and azobenzene was investigated. The reaction of 1 with AcQ in 1:1 molar ratio proceeds via two-electron reduction of AcQ to give (dpp-Bian)Ga(μ2-AcQ)Ga(dpp-Bian) (2), in which diolate [AcQ](2-) acts as "bracket" for the Ga-Ga bond. The interaction of 1 with AcQ in 1:2 molar ratio proceeds with an oxidation of the both dpp-Bian ligands as well as of the Ga-Ga bond to give (dpp-Bian)Ga(μ2-AcQ)2Ga(dpp-Bian) (3).
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G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina 49, Nizhny Novgorod 603950, Russian Federation.
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G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinina 49, 603950 Nizhny Novgorod, Russia.
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