The Si-Si effect on ionization of beta-disilanyl sulfides and selenides.
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.
Glass
Richard S
RS
Department of Chemistry, The University of Arizona, Tucson, AZ 85721, USA. rglass@u.arizona.edu
Block
Eric
E
Lorance
Edward
E
Zakai
Uzma I
UI
Gruhn
Nadine E
NE
Jin
Jin
J
Zhang
Shao-Zhong
SZ