Monosilane (SiH4) is far less well behaved than its carbon analogue methane (CH4). 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 SiH4 in academic laboratories are extremely rare and methodologies based on SiH4 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 SiH4. We disclose here that the commercially available Lewis acid tris(pentafluorophenyl)borane, B(C6F5)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 SiH4 as a building block for the preparation of various hydrosilanes.
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This research was supported by the Alexander von Humboldt Foundation (postdoctoral fellowship to A.S., 2014‒2015) and the Deutsche Forschungsgemeinschaft (Oe 249/11-1). M.O. is indebted to the Einstein Foundation (Berlin) for an endowed professorship. The authors thank E. Irran for the X-ray analysis, S. Kemper for expert advice on NMR spectroscopy, as well as L. Omann and O. Yahiaoui for experimental support (all TU Berlin).
The authors declare no competing financial interests.
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Simonneau, A., Oestreich, M. Formal SiH4 chemistry using stable and easy-to-handle surrogates. Nature Chem 7, 816–822 (2015). https://doi.org/10.1038/nchem.2329
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