Molecular Inorganic Silicon Chemistry: Steric Effect on the Formation, Structure, and Reactions of Pentacoordinate Siliconium Ion Salts

Inna Kalikhman, Boris Gostevskii, Akella Sivaramakrishna, Daniel Kost, Nikolaus Kocher, Dietmar Stalk

Research output: Chapter in Book/Report/Conference proceedingChapterpeer-review

Abstract

Bulky monodentate ligands affect the structure and reactivity of siliconium ion complexes in several ways: they enhance ionization, they promote a methyl halide elimination reaction, and they severely distort complex geometries. The latter effect enabled the assembly of a reaction coordinate model for the Berry pseudorotation, composed of crystal structures with varying NSiN and OSiO bond angles. In a competition between opposing effects of electron withdrawal by CF3 and steric bulk of a cyclohexyl ligand in the same molecule, a nonionic dissociation of the dative N→Si bond was observed.

Original languageEnglish
Title of host publicationOrganosilicon Chemistry VI
Subtitle of host publicationFrom Molecules to Materials
PublisherWiley-VCH Verlag GmbH
Pages297-302
Number of pages6
ISBN (Print)3527312145, 9783527312146
DOIs
StatePublished - 21 May 2008

Keywords

  • Dative-Bond dissociation
  • Hexacoordinate
  • Hypervalent compounds
  • Model berry pseudorotation

ASJC Scopus subject areas

  • General Chemistry

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