The Si-Si effect on ionization of β-disilanyl sulfides and selenides

Richard S. Glass, Eric Block, Edward Lorance, Uzma I. Zakai, Nadine E. Gruhn, Jin Jin, Shao Zhong Zhang

Research output: Contribution to journalArticlepeer-review

14 Scopus citations

Abstract

The ionization energies of conformationally constrained, newly synthesized β-disilanyl sulfides and selenides were determined by photoelectron spectroscopy. These ionization energies reflect substantial (0.53-0.75 eV) orbital destabilizations. The basis for these destabilizations was investigated by theoretical calculations, which reveal geometry-dependent interaction between sulfur or selenium lone pair orbitals and σ-orbitals, especially Si-Si σ-orbitals. These results presage facile redox chemistry for these compounds and significantly extend the concept of σ-stabilization of electron-deficient centers.

Original languageEnglish (US)
Pages (from-to)12685-12692
Number of pages8
JournalJournal of the American Chemical Society
Volume128
Issue number39
DOIs
StatePublished - Oct 4 2006
Externally publishedYes

ASJC Scopus subject areas

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

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