Interaction of C-Si, C-Sn, and Si-Si sigma-bonds with chalcogen lone pairs

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.