Potential energy profiles for the unimolecular reactions of [C₃H₇S]⁺ Ions

Abstract

Abstract Appearance energies were measured for several types of [C 3 H 7 S] + ions. From these appearance energy values the heats of formation of the ions were calculated. For the isomeric ions that could not be generated in the mass spectrometer, the heats of formation were estimated by means of the isodesmic substitution method. Transition state energies for the decomposition to C 2 H 4 and [CH 3 S] + along two pathways were determined from the appearance energies of these ions. Using the energy values, potential energy diagrams were constructed for the rearrangements and decompositions of the [C 3 H 7 S] + ions. A supplementary 13 C Clabelling experiment is described for the determination of the rearrangement pathway of [CH 3 CH 2 CHSH] + ions prior to decomposition.