THE PHOTOELECTRON-SPECTRA OF DIMETHOXYSULFANE AND DIMETHOXYDISULFANE

The He(I) photoelectron spectra of dimethoxysulfane (1) and dimethoxyd isulfane (2) have been recorded. The lowest energy ionizations in the PE spectrum of 1 can be explained by assuming C2 symmetry. They can be described as arising from linear combinations between the 3p lone-pai r at sulfur and 2p lone-pairs at the oxygen atoms. A comparison betwee n the calculated MO sequence of 2 for different conformations and the first PE bands shows a good agreement with an OSSO torsional angle nea r 90-degrees. The highest occupied MOs of 2 can be described as linear combinations between the 3p MOs of the S2 unit and linear combination s between the 2p AOs of the oxygen atoms.