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Cationic Si−H−Si Bridges in Polysilanes: Their Detection and Targeted Formation in Stable Ion Studies
Author(s) -
Albers Lena,
Baumgartner Judith,
Marschner Christoph,
Müller Thomas
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600116
Subject(s) - cationic polymerization , silylation , intramolecular force , chemistry , ion , yield (engineering) , lewis acids and bases , hydrogen , ionization , photochemistry , polymer chemistry , materials science , organic chemistry , catalysis , metallurgy
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.