Chalcogenides of aluminium(III) and gallium(III) derived from Lewis base adducts of alane and gallane
作者:Warren J. Grigsby、Colin L. Raston、Vicki-Anne Tolhurst、Brian W. Skelton、Allan H. White
DOI:10.1039/a802243g
日期:——
Reductive cleavage of (ER)2 by [GaH3L], L = NMe3 or P(C6H11)3, afforded [Ga(TePh)3(NMe3)], [Ga(SeEt)3(NMe3)] and [Ga(TePh)3P(C6H11)3}]; the latter was also prepared by the reaction of [GaH2ClP(C6H11)3}] with LiTePh. They have slightly disordered tetrahedral metal centres, established in the solid for [Ga(TePh)3(NMe3)] and [Ga(TePh)3P(C6H11)3}], and in the structure of the aluminium analogue, [Al(SePh)3(NMe3)], which was also determined. Reaction of [GaH2ClP(C6H11)3}] with Li2Se afforded dinuclear trans-[GaCl(µ-Se)[P(C6H11)3]}2] (minor product) which is centrosymmetric with distorted tetrahedral metal centres associated with a planar Ga2Se2 ring system. Treatment of trans-[AlH(µ-Se)(NMe3)}2] with tmen (=N,N,N′,N′-tetramethylethane-1,2-diamine), or [AlH3(tmen)}∞] with elemental selenium, afforded polymeric [[AlH(µ-Se)]2(tmen)}∞]. Cleavage of (EPh)2 by trans-[AlH(µ-Se)(NMe3)}2] gave trans-[Al(µ-Se)(EPh)(NMe3)}2], E = S, Se or Te, also as centrosymmetric dinuclear species with planar Al2Se2 ring systems. Reaction of trans-[AlH(µ-Se)(NMe3)}2] with 2 equivalents of NH(SiMe3)2 or 6-methyl-2-trimethylsilylaminopyridine gave the secondary amine metallated products trans-[Al(µ-Se)[N(SiMe3)2](NMe3)}2] (structurally authenticated as a centrosymmetric dinuclear species) and [Al(µ-Se)(NC5H3NSiMe3-2-Me-6)}2].
(ER)2 通过 [GaH3L]、L = NMe3 或 P(C6H11)3 还原裂解,得到 [Ga(TePh)3(NMe3)]、[Ga(SeEt)3(NMe3)] 和 [Ga(TePh) 3P(C6H11)3}];后者也是通过[GaH2ClP(C6H11)3}]与LiTePh反应制备的。它们具有稍微无序的四面体金属中心,在固体中建立 [Ga(TePh)3(NMe3)] 和 [Ga(TePh)3P(C6H11)3}],以及在铝类似物的结构中,[Al (SePh)3(NMe3)],也进行了测定。 [GaH2ClP(C6H11)3}] 与 Li2Se 的反应得到双核反式-[GaCl(μ-Se)[P(C6H11)3]}2](次要产物),其与扭曲的四面体金属中心中心对称平面 Ga2Se2 环系统。用 tmen (=N,N,N′,N′-四甲基乙烷-1,2-二胺) 或 [AlH3(tmen)}∞ 处理反式-[AlH(μ-Se)(NMe3)}2] ] 与元素硒,得到聚合物 [[AlH(μ-Se)]2(tmen)}∞]。 (EPh)2 被反式-[AlH(μ-Se)(NMe3)}2]裂解得到反式-[Al(μ-Se)(EPh)(NMe3)}2],E = S、Se 或Te,也是具有平面 Al2Se2 环系的中心对称双核物种。反式-[AlH(μ-Se)(NMe3)}2]与2当量的NH(SiMe3)2或6-甲基-2-三甲基甲硅烷基氨基吡啶反应,得到仲胺金属化产物反式-[Al(μ-Se) )[N(SiMe3)2](NMe3)}2](结构上被证实为中心对称双核物种)和[Al(μ-Se)(NC5H3NSiMe3-2-Me-6)}2]。