SYNTHESIS AND REACTIVITY OF TITANOCENE AND ZIRCONOCENE TRIFLATES

The synthesis of triflate derivatives of titanocene and zirconocene fr om the corresponding dimethyl complexes and triflic acid (HOTf) is des cribed. Comproportionation of Cp(2)M(OTf)(2) with Cp(2)MX(2) gives Cp( 2)M(OTf)X (M = Ti, X = Cl, F, Me; M = Zr, X = Cl, Me, BH4). Cp(2)TiMe( OTf) reacts with ROH (R = Me, Me(3)Si or Me(2)(t)BuSi) to give Cp(2)Ti OR(OTf). Cp(2)TiMe(OTf) and Cp(2)TiOSiMe(3)(OTf) react with H2O to giv e the ore-bridged dimer (Cp(2)TiOTf)(2)(mu-O). The triflate in Cp(2)Ti X(OTf)(X = Cl, F, Me, OSiMe(3)) is substituted by (-)OSiMe(3) to give compounds Cp(2)TiX(OSiMe(3)). Cp(2)Ti(OMe)OR (R = Me, SiMe(3)) could n ot be obtained.