SYNTHESIS AND CHARACTERIZATION OF (ETA(5)-CYCLOPENTADIENYL)(ETA(5)-RING)TITANIUM ALKYL (RING EQUALS INDENYL OR C(5)H(4)BU(T)) COMPLEXES - CRYSTAL AND MOLECULAR-STRUCTURE OF RACEMIC [TI(ETA(5)-C5H5)(ETA(5)-C9H7)(CH(2)SIME(3))CL]

New, selective and high-yielding preparations of the mixed-ring comple xes [Ti(eta(5)-C5H5)(eta(5)-C9H7)Cl-2] and [Ti(eta(5)-C5H5)(eta(5)-C(5 )H(4)Bu(t))Cl-2] are reported. These have been used to prepare a range of mono- and disubstituted titanium(IV) alkyl and benzenethiolate com plexes of the form [Ti(eta(5)-C5H5)(eta(5)-ring)(CH(2)SiMe(3))Cl] and [Ti(eta(5)-C5H5)(eta(5)-ring)R(2)] (ring = indenyl or C(5)H(4)Bu(t); R = Me, CH(2)Ph, CH(2)SiMe(3) or SPh). While the indenyl ligand in the racemic, chiral-at-metal complex [Ti(eta(5)-C5H5)(eta(5)-C9H7)(CH(2)Si Me(3))Cl] is bound in an eta(5) fashion, X-ray structural data clearly indicate that there is some 'eta(3) ring-slip' character to the bondi ng. The NMR and nuclear Overhauser effect experiments conducted on ta( 5)-C5H5)(eta(5)-C(5)H(4)Bu(t))(CH(2)SiMe(3))Cl] demonstrate hindered r otation around the Ti-C(5)H(4)Bu(t) bond and show the geometry to be f ixed such that the Bu(t) and SiMe(3) groups are remote.