Synthesis, characterization, and organic chemistry of an edge-bridged half-open titanocene

The synthesis and characterization of an edge-bridged half-open titanocene, Ti(C5H5)(6,6-dmch)(PMe3) (dmch=dimethylcyclohexadienyl) is described. In this complex one observes significantly shorter TiC bonds to the dmch ligand as compared to the C5H5 ligand. The dmch ligand also behaves as a nucleophile toward ketones, yielding a variety of products with unusual regio- and stereochemistries.