Vibrational and electronic spectroscopy of neutral antimony coordination compounds of the 1,3-dithiole-2-thione-4,5-dithiolate (dmit).

The S 1s X-ray absorption near edge structure (XANES) and X-ray photoelectron spectra (XPS) of the neutral complexes [SbL(dmit)] (L = Br or I; dmit =1,3-dithiole-2-thione-4,5-dithiolate) have been measured using tunable synchrotron radiation. The valence shell electronic excitation by ultraviolet-visible (UV-vis) spectroscopy and the infrared vibrational spectra are presented and analyzed. The UV-vis results lead to an assignment of bands at 400 nm as π(Sm) → π*(C═S), where S(m) is the thiolate sulfur. The corresponding S 1s → π*(C═S) transition was identified at 2468.3 eV. Ab initio calculations, within the improved virtual orbital (IVO) method, carried out with the GSCF3 program, were applied to establish a complete and accurate spectral assignment. It has been the first attempt to apply such methodology for dmit coordination compounds, and very consistent results were obtained.

Rearrangement, nucleophilic substitution, and halogen switch reactions of alkyl halides over NaY Zeolite: formation of the bicyclobutonium cation inside the zeolite cavity.

Rearrangement and nucleophilic substitution of cyclopropylcarbinyl bromide over NaY and NaY impregnated with NaCl was observed at room temperature. The first-order kinetics are consistent with ionization to the bicyclobutonium cation, followed by internal return of the bromide anion or nucleophilic attack by impregnated NaCl to form cyclopropylcarbinyl, cyclobutyl, and allylcarbinyl chlorides. The product distribution analysis revealed that neither a purely kinetic distribution, similar to what is found in solution, nor the thermodynamic ratio, which favors the allylcarbinyl halide, was observed. Calculations showed that bicyclobutonium and cyclopropylcarbinyl carbocations are minimal over the zeolite structure, and stabilized by hydrogen bonding with the framework structure. A new process of nucleophilic substitution is reported, namely halogen switch, involving alkyl chlorides and bromides of different structures. The reaction occurs inside the zeolite pores, due to the confinement effects and is an additional proof of carbocation formation on zeolites. The results support the idea that zeolites act as solid solvents, permitting ionization and solvation of ionic species.