UV-photoelectron spectroscopy and MS-CASPT2/CASSCF study of the thermolysis of azidoethyl-methyl sulfide: Characterization and mechanism of the formation of <i>S-</i>methy<i>l-N-</i>sulfenylethanimine

Abstract

The thermal decomposition of azidoethyl methyl sulfide was studied by real-time UV-photoelectron spectroscopy (UV-PES) at temperatures ranging from 773 to 1023 K. Different ionization energies were obtained using density functional theory calculations to assign UV-PES spectra. The complete active space self-consistent field and multistate second-order perturbation methods were used to predict the formation of different species present in the thermal decomposition process. N2 and S-methyl-N-sulfenylethanimine are generated at 773 K. The first step of the reaction is the dissociation of the molecule into nitrene and nitrogen. The spin state (singlet or triplet) of nitrene formed in the first step of the reaction is temperature-dependent. At low temperatures (T ≤ 650 K), both states are formed with almost the same probability; in contrast, at high temperatures (T ≥ 1000 K), singlet nitrene is the majority intermediate. From this singlet nitrene, three stable reaction products were detected in the experiments: an imine derivative, a four-member cyclic derivative, and a sulfenyl derivative.