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Ylenes in the M~(II)→Si~(IV) (M=Si, Ge, Sn) coordination mode

机译:M〜(II)→Si〜(IV)(M = Si,Ge,Sn)配位模式下的分子

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The reaction of the methimazolyl (mt, i.e., 2-mercapto-1-methylimidazolide) substituted silane Si(mt)_4 with SnCl_2 and GeCl _2 in dioxane affords the paddlewheel-shaped complexes [ClSi(μ-mt)_4MCl] (M=Sn (1) and Ge (2), respectively). These compounds represent the first crystallographically characterized hexacoordinate silicon complexes comprising a Sn or Ge atom in the Si coordination sphere. An attempt to synthesize the related silicon compound 3 [ClSi(μ-mt) _4SiCl] instead afforded the trisilane [ClSi(μ-mt) _4Si-SiCl_3] (3a), which provides the first crystallographic evidence for the feasibility of oligosilanes with adjacent hexacoordinate Si atoms. One of the hexacoordinate Si atoms of 3a features the unprecedented (Si_2S_4)Si skeleton. Natural bonding orbital (NBO) analyses of compounds 1, 2, 3a (and the target compound 3) revealed characteristics of M~(II)→Si~(IV) (for 2 and 3) or M~I→Si ~(IV) (for 3a) dative bonding in the systems with M=Si and Ge, whereas compound 1 exhibits a covalent Sn~(III)-Si~(III) bond. The first structurally evidenced oligosilane with two hexacoordinate Si atoms exhibits electronic features of a Cl_3SiSi→SiCl dative bond, as shown by a natural bonding orbital analysis. Whereas the same features apply to a related methimazolide-bridged ClGe~(II)→Si~(IV)Cl complex, the corresponding Sn-Si system exhibits pronounced features of a covalent Sn ~(III)-Si~(III) bond.
机译:甲硫唑基(mt,即2-巯基-1-甲基咪唑啉)取代的硅烷Si(mt)_4与SnCl_2和GeCl _2在二恶烷中的反应提供了桨轮状复合物[ClSi(μ-mt)_4MCl](M =分别为Sn(1)和Ge(2)。这些化合物代表在Si配位球中包含Sn或Ge原子的第一晶体学表征的六配位硅配合物。尝试合成相关的硅化合物3 [ClSi(μ-mt)_4SiCl]得到了三硅烷[ClSi(μ-mt)_4Si-SiCl_3](3a),这为低聚硅烷与相邻硅烷的可行性提供了第一个晶体学证据。六配位硅原子。 3a的六配位Si原子之一具有前所未有的(Si_2S_4)Si骨架。化合物1、2、3a(和目标化合物3)的自然键合轨道(NBO)分析显示了M〜(II)→Si〜(IV)(对于2和3)或M〜I→Si〜(IV )(对于3a)在具有M = Si和Ge的体系中进行键合,而化合物1具有共价的Sn〜(III)-Si〜(III)键。第一个具有两个六配位Si原子的结构证明的低聚硅烷表现出Cl_3SiSi→SiCl配位键的电子特征,如自然键合轨道分析所示。尽管相同的特征适用于相关的甲硫咪唑桥联的ClGe〜(II)→Si〜(IV)Cl络合物,但相应的Sn-Si系统却表现出共价的Sn〜(III)-Si〜(III)键的明显特征。

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