The substituted metallocene compounds Cp 2 M(OSO 2 CF 3 ) 2 (Cp=g 5 -C 5 H 5 ; M = Ti, Zr, Hf, Nb, Mo), CpTi(O-SO 2 CF 3 ) 3 AE 0.75(1,2-dimethoxyethane), and the organo-main group compounds (C 6 H 5 ) 3 M¢(OSO 2 CF 3 ) (M¢=Si, Ge), (C 6 H 5 ) 2 Sn(OSO 2 CF 3 ) 2 and (C 6 H 5 ) 3 Sb(OSO 2 CF 3 ) 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(OSO 2 CF 3 ) 3 AE 0.75(1,2-dimethoxyethane) and the organo-germanium triflate show evidence of bidentate CF 3 SO À 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 2 HfCl 2 / Ag(OSO 2 CF 3 ), CpTiCl 3 /Ag(OSO 2 CF 3 ) and (C 6 H 5 ) 2 SiCl 2 /Ag(OSO 2 CF 3 ), are also reported.