Reaction of trimethylsilylacetylenes with antimony pentafluoride under matrix isolation conditions: experimental and computational study

J Org Chem. 2010 Oct 15;75(20):6969-72. doi: 10.1021/jo101185n.

Abstract

Reaction of trimethylsilylacetylenes Me(3)SiC≡CR with SbF(5) in the solid state was investigated using matrix isolation infrared spectroscopy and quantum-mechanical calculations. Two reaction pathways were detected. Replacement of the trimethylsilyl group with SbF(4) produces neutral antimony acetylides F(4)SbC≡CR. Acetylenic bond protonation produces silyl cation 6-R, fully bridged for R = H and SiMe(3). High total charges on the bridging SiMe(3) group and low Me(3)Si-C bond orders to acetylenic moiety, both calculated at the MP4(SDQ)/6-311G(d,p) level of theory, indicate high silyl cation character of these species.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkynes / chemistry*
  • Antimony / chemistry*
  • Fluorides / chemistry*
  • Molecular Dynamics Simulation*
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry
  • Quantum Theory*
  • Trimethylsilyl Compounds / chemistry*

Substances

  • Alkynes
  • Organometallic Compounds
  • Trimethylsilyl Compounds
  • antimony pentafluoride
  • Antimony
  • Fluorides