Trapping Experiments on a Trichlorosilanide Anion: a Key Intermediate of Halogenosilane Chemistry.
Treatment of Si2Cl6with [Et4N][BCl4] in CH2Cl2furnished the known products of a chloride-induced disproportionation reaction of the disilane, such as SiCl4, [Si(SiCl3)3]-, and [Si6Cl12·2Cl]2-. No Si-B-bonded products were detectable. In contrast, the addition of Si2Cl6to [Et4N][BI3Cl] afforded the Si-B adduct [Et4N][I3SiBI3]. Thus, a quantitative Cl/I exchange at the silicon atom accompanies the trihalogenosilanide formation. [Et4N][I3SiBI3] was also accessible from a mixture of Si2I6, [Et4N]I, and BI3. According to X-ray crystallography, the anion [I3SiBI3]-adopts a staggered conformation with an Si-B bond length of 1.977(6) Å. Quantum-chemical calculations revealed a polar covalent Si-B bond with significant contributions from intramolecular I···I dispersion interactions.
Institut für Anorganische Chemie, Goethe-Universität Frankfurt am Main , Max-von-Laue-Straße 7, 60438 Frankfurt am Main, Germany.
Julian
J
Teichmann
Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universität Bonn , Beringstraße 4, 53115 Bonn, Germany.
Markus
M
Bursch
Institut für Anorganische Chemie, Goethe-Universität Frankfurt am Main , Max-von-Laue-Straße 7, 60438 Frankfurt am Main, Germany.
Benedikt
B
Köstler
Institut für Anorganische Chemie, Goethe-Universität Frankfurt am Main , Max-von-Laue-Straße 7, 60438 Frankfurt am Main, Germany.
Michael
M
Bolte
Institut für Anorganische Chemie, Goethe-Universität Frankfurt am Main , Max-von-Laue-Straße 7, 60438 Frankfurt am Main, Germany.
Hans-Wolfram
HW
Lerner
Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universität Bonn , Beringstraße 4, 53115 Bonn, Germany.
Stefan
S
Grimme
Institut für Anorganische Chemie, Goethe-Universität Frankfurt am Main , Max-von-Laue-Straße 7, 60438 Frankfurt am Main, Germany.
Matthias
http://orcid.org/0000-0001-5806-8276
M
Wagner