Metallocene and organo-main group trifluoromethanesulfonates

• The substituted metallocene compounds Cp2M(OSO 2CF3)2 (Cp=η5-C 5H5; M = Ti, Zr, Hf, Nb, Mo), CpTi(OSO2CF 3)3 • 0.75(1,2-dimethoxyethane), and the organo-main group compounds (C6H5)3M′(OSO 2CF3) (M′=Si, Ge), (C6H5) 2Sn(OSO2CF3)2 and (C 6H5)3Sb(OSO2CF3) 2, were synthesized from the corresponding chloride or bromide compounds and silver trifluoromethanesulfonate (triflate) and characterized spectroscopically, including a detailed analysis of their IR spectra. Triflate coordination is typically monodentate, but CpTi(OSO2CF 3)3 • 0.75(1,2-dimethoxyethane) and the organo-germanium triflate show evidence of bidentate CF3SO 3 - ligands and are likely to have polymeric structures. Conductance measurements in nitromethane, acetone and acetonitrile have demonstrated the ease of triflate substitution, with a limited kinetic study of acetone solvation of the Ti and Hf compounds supporting an associative pathway. Three new catalysts for the polymerization of tetrahydrofuran, Cp 2HfCl2/Ag(OSO2CF3), CpTiCl 3/Ag(OSO2CF3) and (C6H 5)2SiCl2/Ag(OSO2CF3), are also reported.

Keyword

Acetone

Catalysts

Esters

Polymerization

Reaction kinetics

Synthesis (chemical)

Metallocene compounds

Solvation

Tetrahydrofuran

Olefins

Publication and Content Type

ref (subject category)

art (subject category)