| This project involves the formation of eight novel sulfur-based radical cations from small organic molecules in a quadrupole ion trap (QIT) mass spectrometer using one of two different methods. In the first, a thiol analyte is oxidized in solution into a disulfide dimer, protonated during electrospray ionization (ESI), and then the S-S bond is homolytically cleaved by collision-induced dissociation (CID), resulting in a radical cation. In the second method, a ternary metal complex is formed in solution between an analyte, copper (II) ion, and terpyridine. During CID, electron transfer and coordinative bond cleavage between the analyte and copper (II) ion generates a sulfur-centered radical cation. Ion-molecule reactions (IMR) were then performed to characterize the intrinsic gas-phase reactivity of each radical species. The results were compared to DFT calculations of C-S bond length, spin density, and atomic charges for each radical ion, and to the reactivity of other sulfur-based radical ions. |
