DFT(B3LYP) calculations of silatranes and their radical cations. First ionization potentials

Abstract

DFT(B3LYP) and 2 quantum chemical calculations have been performed for 1-substituted silatranes XSi(OCH2CH2)N (X = H, CH3, CH2Cl, F), their radical cations, and first ionization potentials (IP1) of these silatranes. The calculated values of IP1 agree well with the experiment and make it possible to assign the first band to IP1 in the photoelectron spectra. Analysis of spin density distribution and electronic charges in the radical cations suggests that ionization occurs mainly due to the lone electron pair of nitrogen, participating in intramolecular coordination. The N → Si interaction is broken, and the N...Si distance increases to 335–340 pm.