Synthesis and Characterisation of Bridged Titanocene Oxido Complexes and Their Reactions with Water

The synthesis of two pyridine-stabilised ansa-titanocene oxido complexes is described. Oxidation of the titanocene sources (Cp2Ti)-Ti-b(eta(2)-Me3SiC2SiMe3) (Cp-2(b) = bridged eta(5)-cyclopentadienyl, 1a and 1b) with nitrous oxide yields corresponding oxido compounds 2a and 2b, respectively, in high yields. These can be hydrolysed to give dihydroxido complexes 3a and 3b, respectively, without the formation of by-products. The hydrolysis reaction was monitored by means of in situ IR spectroscopy. Hitherto unknown complexes 2a and 2b were fully characterised, and their molecular structures are reported in this paper.