Insertion of 2,3-dihydrothiophene into platinum and osmium hydrides: A model for reactions occurring during thiophene hydrodesulfurization

Article abstract of DOI:10.1021/om00110a005

Reaction of HPt(acetone)(PEt₃)₂⁺ with 2,3-DHT results in the formation of the sulfur-coordinated 2,3-DHT compound I. Subsequent rearrangement by slow insertion of the 2,3-DHT olefin into the Pt-H bond gives (Chemical Equation Presented) II, which was characterized by an X-ray diffraction study. Compound II reacts with H₂ at 150°C to yield butane. A tungsten analogue (VIIIa) of II is prepared from the reaction of CpW(CO)₃^- with 2-chlorotetrahydrothiophene followed by photolytic decarbonylation. The reaction of VIIIa with HCl yields an (Chemical Equation Presented) unstable tetrahydrothiophene (THT) complex IX. These reactions serve as models for the conversion of thiophene to THT and C₄ products. Insertion of 2,3-DHT into a metal cluster hydride is achieved in the (Chemical Equation Presented) reaction of 2,3-DHT with H₂Os₃(CO)₉PPh₃ to form X whose structure was established by X-ray diffraction.