title: Interaction of C-Si, C-Sn, and Si-Si sigma-bonds with chalcogen lone pairs.
abstract: The ability of neighboring C-Si, C-Sn, and Si-Si groups in conformationally constrained cyclic molecules to reduce the lowest ionization energies of sulfur, selenium, and tellurium compounds has been determined by charge-transfer spectroscopy of complexes with tetracyanoethylene. For selected compounds, ionization energies were determined by gas-phase photoelectron spectroscopy. The lowest ionization energies measured by photoelectron spectroscopy, with one exception, correlate with the charge-transfer spectroscopic data. In addition, theoretical analysis has provided insight into the photoelectron spectra and the geometry-dependent interaction between C-Si or C-Sn bonds and chalcogen lone pairs. Substantial lowering of ionization energies is found which is anticipated to have important consequences in the chemistry of these and related species.
authors.affiliation: Department of Chemistry, The University of Arizona, Tucson, Arizona 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: Nadine E
authors.initials: NE
authors.lastname: Gruhn
authors.forename: Jin
authors.initials: J
authors.lastname: Jin
authors.forename: Edward
authors.initials: E
authors.lastname: Lorance
authors.forename: Uzma I
authors.initials: UI
authors.lastname: Zakai
authors.forename: Shao-Zhong
authors.initials: SZ
authors.lastname: Zhang