Diastereomeric hexacoordinate silicon complexes: Preparation, structure and epimerization

Olga Girshberg, Inna Kalikhman, Dietmar Stalke, Bernhard Walfort, Daniel Kost

Research output: Contribution to journalArticlepeer-review

10 Scopus citations


The synthesis of a neutral hexacoordinate silicon complex (6) with a chiral silicon and an adjacent chiral carbon center, via an intramolecular nucleophilic displacement, is described. 6 exists in a mixture of two diastereomers. One of the diastereomers has been characterized by an X-ray crystallographic analysis, and is found to have a nearly octahedral geometry about the silicon. 6 undergoes two intramolecular ligand-site exchhange processes, observable by NMR spectroscopy: reversible dissociation of the N-Si dative bond, leading to interchange of the N-methyl groups (ΔG*=16. 7±0.2kcalmol-1 at 365 K), and inversion of configuration at the silicon center, measured by selective inversion recovery NMR spectroscopy (21.0kcalmol-1 at 350 K).

Original languageEnglish
Pages (from-to)259-264
Number of pages6
JournalJournal of Molecular Structure
Issue number1-3
StatePublished - 16 Dec 2003


  • Hypercoordination
  • Inversion of configuration
  • Molecular rearrangement
  • Selective inversion recovery NMR
  • Silicon

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy
  • Organic Chemistry
  • Inorganic Chemistry


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