On the photoelectron and ultraviolet spectra of molecules containing a divalent sulfur atom and a carbonyl group separated by a methylene group

Abstract

Can. J. Chem. 54, 3026 (1976).Photoelectron spectra show that in CH3SCH2COCH3 the sulfur and carbonyl lone pair orbitals (S,O) are both stabilized with respect to the compounds containing S or CO only. This is in keeping with the observed values of the basicity constants. The ultraviolet absorption spectra contain the expected T * c 0 and a* t S bands and give evidence for a significant amount of mixing between the excited orbitals. P. R. OLIVATO, H. VIERTLER, B. WLADISLAW, K. C. COLE et C. SANDORFY. Can. J. Chern. 54, 3026 (1976).Nous avons mis en evidence par la mesure de spectres photoelectroniques que dans la molecule CH3SCH2COCH3 les orbitales des doublets libres du soufre et du carbonyle sont toutes deux stabilisies par rapport B leur valeur dans les molecules respectives qui ne contiennent que S ou CQ. Cela esten accord avec les valeurs observies des constantes de basiciti. Les frequences des bandes T * + 0 et U * t S dans le spectre d'absorption ultraviolet indiquent qu'il se produit un melange apprkiable entre les orbitales excities.

Sobre as interações eletrônicas em algumas ciclanonas e em 2-ciclopentenona, substituídas em α por um átomo de enxofre

“…~ P r e se n ta m d u a5 b a n das de absorção, uma em ca. de 300 rime outra em 2•50 nme demons .. tram, no grifico, que no Caso de 3-tiacicloheptanona o espe~ tro não e uma simples sobreposiçã: o dos .…”