Cationic Si−H−Si Bridges in Polysilanes: Their Detection and Targeted Formation in Stable Ion Studies |
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| Authors: | Dr Lena Albers Dr Judith Baumgartner Prof Christoph Marschner Prof Thomas Müller |
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| Institution: | 1. Institut für Chemie, Carl von?Ossietzky Universit?t Oldenburg, Oldenburg, Germany;2. Institut für Chemie, Universit?t Graz, Graz, Austria;3. Institut für Anorganische Chemie, Technische Universit?t Graz, Graz, Austria |
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| Abstract: | The ionization of 1,1‐dihydridocyclopentasilane 7 has been found to yield the cyclic polysilanylsilyl cation 8 instead of the expected hydrogen‐substituted silylium ion 6 . The silyl cation 8 is stabilized by the formation of an intramolecular Si?H?Si bridge, which also provides the thermodynamic driving force for its formation. In general, the preference for the formation of Si?H?Si bridges can be used to scavenge and identify transient intermediates in the Lewis acid induced rearrangement of polysilanes. The validity of this concept has been demonstrated for one central step in this chemistry, the ring‐contraction reaction of cyclohexasilanes to form silylcyclopentasilanes. |
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| Keywords: | cations density functional calculations polysilanes reaction mechanisms silicon |
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