Reductive Elimination of Hydrogen from Bis(trimethylsilyl)methyltin Trihydride and Mesityltin Trihydride.
Reductive Elimination of Hydrogen from Bis(trimethylsilyl)methyltin Trihydride and Mesityltin Trihydride.
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DOI：
10.1002/chem.201605317
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发表时间：
2017-02
期刊：
影响因子：
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通讯作者：
Jakob‐Jonathan Maudrich;Christian P. Sindlinger;Frederik S. W. Aicher;K. Eichele;H. Schubert;L. Wesemann
中科院分区：
文献类型：
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作者：
Jakob‐Jonathan Maudrich;Christian P. Sindlinger;Frederik S. W. Aicher;K. Eichele;H. Schubert;L. Wesemann
合成了烷基锡三氢化物[(Me3 Si)2 CHSnH3 ]并研究了该物质中氢的还原消除。甲基取代的N-杂环卡宾根据化学计量和溶剂与有机三氢化物反应，产生一系列还原消除和脱氢锡-锡键形成的产物。除了氢化烷基锡(II)的卡宾加合物的表征之外，还分离了一条Sn4链，该链包含两个甲锡烷基-亚甲锡位点，每个位点均作为NHC加合物进行稳定。完全脱氢得到卡宾稳定的二锡炔或类金属 Sn9 簇盐。还用过量的二乙基甲胺实现了氢的还原消除，得到烷基锡(II)氢化物，为无路易斯碱四聚体[(RSnH)4]。通过氢消除在低温下形成簇的方法也被转移到异亚丙基取代的三氢化锡MesSnH3上。在这种情况下，[(MesSn)10]显示出[5]棱柱烷结构，以良好的产率分离并表征。报道了螺旋桨型簇 [Trip6 Sn6 ] 的 NMR 光谱特征。
Alkyltin trihydride [(Me3 Si)2 CHSnH3 ] was synthesized and the reductive elimination of hydrogen from this species was investigated. A methyl-substituted N-heterocyclic carbene reacts with the organotrihydride in dependence on stoichiometry and solvent to give a series of products of the reductive elimination and dehydrogenative tin-tin bond formation. Besides characterization of the carbene adduct of the alkyltin(II) hydride, a Sn4 chain was also isolated, encompassing two stannyl-stannylene sites, which are stabilized each as NHC-adducts. Complete dehydrogenation resulted to give either a carbene-stabilized distannyne or a metalloid Sn9 -cluster salt. Reductive elimination of hydrogen was also achieved with an excess of diethylmethylamine to give the alkyltin(II) hydride as a Lewis base free tetramer [(RSnH)4 ]. The method of cluster formation at low temperatures by hydrogen elimination was also transferred to the mesityl-substituted tin trihydride MesSnH3 . In this case [(MesSn)10 ], showing a [5]prismane structure, was isolated in good yield and characterized. NMR spectroscopic features of the propellane-type cluster [Trip6 Sn6 ] are reported.