n -杂环卡宾稳定的GaH2SbH2母单体

Robert Szlosek, Kevin Dollberg, Gábor Balázs, Michael Seidl, Carsten von Hänisch, Manfred Scheer
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引用次数: 0

摘要

介绍了二苯基三烷IDipp·GaH2Sb(SiMe3)2 (1a)和IDipp·BH2Sb(SiMe3)2 (1b)的合成和表征。1a是分离仅由路易斯碱(LB)稳定的二苯乙烯gallane分子单体的第一个例子。虽然1a中的{SiMe3}残基无法被甲醇裂解,但K(18c6)SbH2与LB·EH2X (LB = IDipp, NMe3; E = B, Ga; X = I, OTf)的直接盐分解反应首次以中等产率分离出了亲本化合物IDipp·BH2SbH2 (2a)、Me3N·BH2SbH2 (2b)和IDipp·GaH2SbH2(3)。具体来说,3的合成不仅代表了{gah2shbh2}基序作为迄今为止已知最重的类乙烯亲本基团13/15元素组合的首次稳定,而且通过LB验证了其稳定过程,从而获得了第一个立体不受阻碍的初级stibane。所有化合物对空气、光和温度都表现出极强的敏感性。通过核磁共振和红外光谱、单晶x射线结构测定和质谱分析对产物进行了表征,并用密度泛函理论计算对产物的电子结构进行了研究。此外,IDipp·GaCl3与K(18c6) shbh2反应生成产物混合物,其中可以识别出3和前所未有的IDipp·GaH(shbh2)2(4)。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

The Parent GaH2SbH2 Monomer Stabilized by an N-Heterocyclic Carbene

The Parent GaH2SbH2 Monomer Stabilized by an N-Heterocyclic Carbene

The synthesis and characterization of the stibanyltrielanes IDipp·GaH2Sb(SiMe3)2 (1a) and IDipp·BH2Sb(SiMe3)2 (1b) are presented. 1a represents the first example for the isolation of a molecular stibanylgallane monomer stabilized only by a Lewis base (LB). While methanolytic cleavage of the {SiMe3} residues in 1a cannot be achieved, the direct salt metathesis reactions of K(18c6)SbH2 with LB·EH2X (LB = IDipp, NMe3; E = B, Ga; X = I, OTf) afford the isolation of the parent compounds IDipp·BH2SbH2 (2a), Me3N·BH2SbH2 (2b), and IDipp·GaH2SbH2 (3) for the first time in moderate yields. Specifically, the synthesis of 3 not only represents the first stabilization of the {GaH2SbH2} motif as the so far heaviest known ethylene-like parent group 13/15 element combination but also validates its stabilization procedure by a LB to access a first sterically unhindered primary stibane. All compounds display drastic sensitivity toward air, light, and temperature. The products are characterized by NMR and infrared spectroscopy, as well as by single-crystal X-ray structure determination and mass spectrometry and the electronic structure is investigated by density functional theory calculations. Furthermore, the reaction of IDipp·GaCl3 with K(18c6)SbH2 yields a product mixture, in which 3 and the unprecedented IDipp·GaH(SbH2)2 (4) can be identified.

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