Ground-state dissociation pathways for the molecular cation of 2-chlorothiophene: A time-of-flight mass spectrometry and computational study.

Abstract

Halogenated thiophenes are an important class of compounds mostly used in the synthesis of various materials, showing unusual electronic and optical properties. The Thiophene Ring Fragmentation (TRF) process is widely used in synthetic chemistry. In this study, the fragmentation pattern of the molecular cation of halogenated thiophene, namely, 2-chlorothiophene, was monitored to establish its dissociation mechanism. The molecular cation of 2-chlorothiophene was prepared using multiphoton excitation using a laser at 235 nm. Various product ions upon fragmentation of the molecular ion were mass analyzed using time-of-flight mass spectrometry. Laser power dependence studies were also conducted for various product ions to arrive at the dissociation mechanism. Theoretical calculations were carried out to estimate the reaction enthalpies for various reactions and compared with the experimental data available in the literature. The most abundant product ion was observed as the HCS+ radical cation followed by the C3 H3 + ion and the H2 CCCCS+ radical cation. Other product ions such as SCCl+ , ClHCCS+ radical cations were also observed to a lesser extent in the fragmentation pattern of the parent molecular ion. Various dissociation channels were identified and supported with ab initio calculation. It has been inferred that the TRF process is usually initiated by the H/Cl atom transfer process. The appearance energies of the various fragment ions were also estimated theoretically and compared with literature values. In conclusion, the fragmentation pattern of the molecular cation of 2-chlorothiophene was studied and the formation mechanisms of various product ions have been assigned. The appearance energies of the various fragment ions were also calculated. Finally, it is inferred that a TRF process is initiated by the H/Cl atom migration and subsequent ring opening either by C-C or C-S bond cleavage leading to the various isomers and their subsequent fragmentation. The ionization energies were accurately predicted for various species using ab initio calculation.