Dehydrosilylation of ArNHSiH3 with ytterbium(II) amide: formation of a dimeric ytterbium(II) silanimine complex.
Dehydrosilylation of ArNHSiH3 with ytterbium(II) amide: formation of a dimeric ytterbium(II) silanimine complex.
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DOI：
10.1002/anie.201004856
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发表时间：
2010-11
影响因子：
--
通讯作者：
Yang Chen;Hai-bin Song;C. Cui
中科院分区：
文献类型：
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作者：
Yang Chen;Hai-bin Song;C. Cui
SiÀH与镧系烷基和氢化物的键活化可以通过σ键复分解生成氢化物或硅基配合物，这是几个重要催化过程的基本步骤，如硅烷的脱氢聚合和不饱和有机化合物的硅氢化反应虽然已经出现了一些关于烯烃和亚胺的硅氢化反应以及胺与镧系酰胺的脱氢硅基化反应的报道，但关于酰胺与氢硅烷反应的研究仍然很少。已经证明，硅解一个LnÀN键可以得到镧系氢化物，同时形成一个新的SiÀN键与氢硅酰胺配体的镧系配合物的分离和结构表征的相关方法揭示了有趣的agostic β-（SiÀH）···Ln相互作用的存在，这可以被视为理解与金属中心的初始SiÀH配位性质的模式。虽然使用[N (SiMe2H) 2] À和[thbun (SiMe2H)] À配体获得了几种类型的有机镧系氢硅胺配合物，但它们的反应性实际上尚未得到探索一些金属氢化硅胺配合物可以通过SiÀH σ键复分解或金属中心氧化加成转化为相应的硅胺配合物。[6a， f]这些不饱和硅配合物虽然数量很少，但已显示出有趣的结构特征和反应性受这些发现的启发，我们对镧系化学中具有HNÀSiH3键的伯胺硅烷的研究产生了兴趣，因为氢的消除可能发生在镧系硅胺配合物中。此外，伯硅烷通常反应性更强，可能会发生涉及SiÀH键的多重反应，这可能使我们能够研究未知的有机配合物的命运。在这方面，
SiÀH bond activation with lanthanide alkyl and hydride compounds is known to yield hydrides or silyl complexes by σbond metathesis, which is a fundamental step for several important catalytic processes, such as dehydropolymerization of silanes and hydrosilylation of unsaturated organic compounds.[1] Although a few reports on hydrosilylation of alkenes and imines and dehydrogenative silylation of amines with lanthanide amides have appeared,[2] studies on reactions of amides with hydrosilanes are still very scant. It has been shown that silanolysis of a LnÀN bond can give the lanthanide hydride with the formation of a new SiÀN bond.[3] The related approaches on the isolation and structural characterization of lanthanide complexes with hydrosilylamido ligands revealed the existence of interesting agostic β-(SiÀH)··· Ln interactions, which can be viewed as modes for understanding the nature of the initial SiÀH coordination to the metal centers.[4]Although several types of agostic lanthanide hydrosilylamido complexes have been obtained by the employment of [N (SiMe2H) 2] À and [tBuN (SiMe2H)] À ligands, their reactivity has been virtually unexplored.[5] A few metal hydrosilylamido complexes can be converted into the corresponding silanimine complexes by either SiÀH σ-bond metathesis or oxidative addition to the metal centers.[6a, f] These unsaturated silicon complexes, although very rare in number, have been shown to display interesting structural features and reactivity.[6] Inspired by these findings, we became interested in the investigation of primary aminosilanes with an HNÀSiH3 linkage in lanthanide chemistry, as the elimination of hydrogen may take place to give lanthanide silanimine complexes. In addition, primary silanes are normally much more reactive and may undergo multiple reactions involving the SiÀH bonds, which may allow us to study the unexplored fate of agostic complexes. In this vein,