Photoelectron spectra and steric structure 1-methylthio- and 1,7-dimethylthiotricyclo[4.1.0.0(27)]heptanes

The stereoelectronic interaction of the lone electron pair of the sulfur at om (ns) with the pi(1,7) pseudo-pi orbital, which depends on the torsion an gle of the MeS group with respect to the C-S bond, determines the ionizatio n potentials and conformational inhomogeneity of 1-methylthio- and 1,7-dime thylthiotricyclo[4.1.0.0(2,7)]heptanes, The highest occupied molecular orbi tal of the thio derivatives are mainly localized on the sulfur atoms, and t his distinguish these compounds from alkyl-substituted tricyclo[4.1.0.0(2,7 )]heptanes, whose highest occupied molecular orbitals are mainly localized on the C-1 and C-7 atoms.