Gas-phase generation and photoelectron spectra of reactive unsubstituted cycloalkenethiones

The flash vacuum thermolysis of cycloalkenyl allyl sulfides, potential prec ursors of unsubstituted cycloalkenethiones, has been investigated by photoe lectron spectroscopy. This technique allowed us to characterize in the gas phase very reactive species of this series, the conjugated and nonconjugate d cyclopentene and cyclohexenethiones, and to compare the reactivity of the se compounds. The assignment of the PE spectra is supported by electronic s tructure calculations, particularly by the HF method at the MP2 level and t he density functional theory (DFT) using the B3LYP and BP86 functionals wit h the 6-311G(d, p) basis set, (C) 2001 Academic Press.