Electronic structure and stability of pentaorganosilicates

Erik P.A. Couzijn, Andreas W. Ehlers, Marius Schakel, Koop Lammertsma

Research output: Contribution to journalArticlepeer-review

48 Citations (Scopus)

Abstract

The exceptional stability of recently reported pentaorganosilicates is investigated by bond energy analyses. Experimental coupling constants are used to probe their electronic structure, entailing bonds with mixed ionic-covalent character. Our analyses reconfirm that the axial bonds are more prone to heterolytic cleavage than are the equatorial bonds. Aryl substituents provide substantial electronic stabilization by charge delocalization, but cause steric crowding due to ortho-hydrogen repulsion. In contrast, silicates with two ax,eq biaryl groups are not congested. The remaining substituent is confined to an equatorial site, where it is insensitive to elimination. These concepts adequately explain the experimentally observed stability trends and are valuable for designing other stable pentaorganosilicates.

Original languageEnglish
Pages (from-to)13634-13639
Number of pages6
JournalJournal of the American Chemical Society
Volume128
Issue number41
DOIs
Publication statusPublished - 18 Oct 2006
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

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