Formal SiH4 chemistry using stable and easy-to-handle surrogates
Formal SiH4 chemistry using stable and easy-to-handle surrogates
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DOI：
10.1038/nchem.2329
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发表时间：
2015-08
期刊：
影响因子：
21.8
通讯作者：
Antoine Simonneau;M. Oestreich
中科院分区：
文献类型：
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作者：
Antoine Simonneau;M. Oestreich
甲硅烷（SiH 4）的性能远不如它的碳类似物甲烷（CH 4）.它是一种无色气体，作为元素硅的工业相关来源，但其自燃和爆炸性质使其处理和使用具有挑战性。因此，SiH 4在学术实验室中的合成应用非常罕见，基于SiH 4的方法学也不发达。氢硅烷的取代基再分布方法的安全和受控的替代品是期望的，并且环己-1，4-二烯单元作为氢原子的占位符的环己-2，5-二烯-1-基硅烷已被确定为SiH 4的有效替代物。我们在此公开了可商购的刘易斯酸三（五氟苯基）硼烷，B（C 6 F 5）3，能够催化促进Si-H键的释放，同时随后能够在同一锅中氢化硅烷化C-C多重键。净反应是以SiH 4为结构单元的无过渡金属转移硅氢加成反应，用于制备各种氢化硅烷。
Monosilane (SiH 4) is far less well behaved than its carbon analogue methane (CH 4). It is a colourless gas that is industrially relevant as a source of elemental silicon, but its pyrophoric and explosive nature makes its handling and use challenging. Consequently, synthetic applications of SiH 4 in academic laboratories are extremely rare and methodologies based on SiH 4 are underdeveloped. Safe and controlled alternatives to the substituent redistribution approaches of hydrosilanes are desirable and cyclohexa-2, 5-dien-1-ylsilanes where the cyclohexa-1, 4-diene units serve as placeholders for the hydrogen atoms have been identified as potent surrogates of SiH 4. We disclose here that the commercially available Lewis acid tris (pentafluorophenyl) borane, B (C 6 F 5) 3, is able to promote the release of the Si–H bond catalytically while subsequently enabling the hydrosilylation of C–C multiple bonds in the same pot. The net reactions are transition-metal-free transfer hydrosilylations with SiH 4 as a building block for the preparation of various hydrosilanes.