Gas-phase ion-molecule clustering reactions of compounds involving two-center three-electron sulfur-sulfur bonds

The main focus of the work presented in this dissertation is on the bonding interaction and structure of ions containing two-center three-electron (2c-3e) sulfur-sulfur bonds.;In the present studies, the 2c-3e bonding interaction is probed directly in the gas-phase without the interference of solvation effects. The enthalpy and entropy of reaction is determined from the temperature dependence of the equilibrium constants. Equilibrium was established in the following three reactions, which provided insight into the bonding interaction of symmetric 2c-3e S.;Ion-molecule reactions of neat thiirane and neat trimethylene sulfide have previously been shown to result in ring expansions. Here, ion-molecule reactions of trimethylene sulfide radical cation with thiirane also resulted in a ring expansion. It was found that ring expansion occured in the mixed system resulting in formation of a six-membered ring (m/z 138).