title: The Si-Si effect on ionization of beta-disilanyl sulfides and selenides.
abstract: The ionization energies of conformationally constrained, newly synthesized beta-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 sigma-orbitals, especially Si-Si sigma-orbitals. These results presage facile redox chemistry for these compounds and significantly extend the concept of sigma-stabilization of electron-deficient centers.
authors.affiliation: Department of Chemistry, The University of Arizona, Tucson, AZ 85721, USA. rglass@u.arizona.edu
authors.forename: Richard S
authors.initials: RS
authors.lastname: Glass
authors.forename: Eric
authors.initials: E
authors.lastname: Block
authors.forename: Edward
authors.initials: E
authors.lastname: Lorance
authors.forename: Uzma I
authors.initials: UI
authors.lastname: Zakai
authors.forename: Nadine E
authors.initials: NE
authors.lastname: Gruhn
authors.forename: Jin
authors.initials: J
authors.lastname: Jin
authors.forename: Shao-Zhong
authors.initials: SZ
authors.lastname: Zhang