[C2H4OS]>·>+> Radical cations derived from alkyl thioformates: tandem mass spectrometry and molecular orbital calculations
Abstract
[C2H4OS]˙+ radical cations have been generated upon dissociative ionization of some S-alkyl and O-alkyl thioformates and characterized by tandem mass spectrometry methodologies and molecular orbital calculations at the UQCISD(T)/6-311++G(d,p)//UMP2/6–31G(d,p) level. Use of a combination of collisional activation (high and low energy translational energies), neutralization–reionization and ion–molecule reaction experiments performed in a single instrument, combining different magnetic and electric sectors and a radiofrequency-only quadrupole collision cell, led to the identification of distonic radical cations and ion–molecule complexes such as HC+(OH)SCH2˙ and CH3S˙+(H)· · ·CO, beside ions having a more classical structure, HC(S)OCH3˙+ and HC(O)SCH3˙+. Experimental evidence for the existence of the isomeric distonic HC+(SH)OCH2˙ species has not been found, but calculations of the related [C2H4OS]˙+ potential energy surface suggest that the latter ion is stable and likely to play a role in the fragmentation processes.