Photoelectron spectroscopic studies of the electronic structure of some silatranes

Abstract
Ultraviolet photoelectron spectra of 17 substituted silatranes (silatrane = 2,8,9-trioxa-5-aza-1-silabicyclo[3.3.3]undecane), measured for gas-phase samples at convenient temperatures, are presented. The spectra are interpreted using both valence-electron molecular orbital calculations and a composite-molecule model. The first ionization band is in most cases, assigned to the nitrogen lone-pair electrons which comprises the Si .fwdarw. N dative bond. This assignment is verified by the observed sensitivity of the location of this band towards substitution at the silicon atom. The .sigma.SiN ionization energies also correlated with the N 1 s binding energies measured for these compounds.

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