MODELS OF SURFACE-CONFINED METALLOCENE DERIVATIVES

The silsesquioxane [((C6H11)7Si7O9)(OH)3] (LH3) was reacted with [M(C5 H5)2Cl2] (M=Ti, Zr, Hf) and with [Ti(C5H5)Cl3]. The reaction with [Ti( C5H5)Cl3] produced [Ti(C5H5)L], whereas the reaction with [Ti(C5H5)2Cl 2] produced a mixture of [Ti(C5H5)L]n (n = 1, 2) as determined by NMR spectroscopy. Only [Ti(C5H5)L] could be isolated from the mixture. The reaction with [M(C5H5)2Cl2] (M=Zr, Hf) produced oligomeric species wh ich contained no cyclopentadienyl ligands and which were formulated as containing trimeric [M3L4Cl]- anions on the basis of analytical and s pectroscopic data.