A SERIES OF BINUCLEAR AND MONONUCLEAR TI(IV), TI(III), AND TI(II) COMPLEXES CONTAINING THE DIANION AND MONOANION OF BIS(CYCLOPENTADIENYL)METMANE AS LIGAND

The reaction of[CH2(C5H4)(2)]Li-2, 1, with C5H5TiCl3 gives the binucle ar complex [[CH2(C5H4)(2)]-[C5H5TiCl2](2)], 4, which on treatment with Mg/Hg is reduced to the corresponding Ti(III)-Ti(III) derivative ([CH 2(C5H4)(2)][C5H5TiCl](2)), 5 If compound 5 is exposed to air, the ore- bridged species [[CH2(C5H4)(2)]-[C5H5TiCl](2)](mu-O), 6, is formed in excellent yield. [[CH2(C5H4)(2)][TiCl3](2)] 8, which is prepared from [[CH2(C5H4)(2)][TiCl2]], 7, and TiCl4, reacts with [CH2(C5H4)(2)]Na-2, 2, to afford the doubly-bridged complex [[CH2(C5H4)(2)](2)[TiCl2](2)] 9, which is reduced with Mg/Hg to [[CH2(C5H4)(2)](2)[TiCl](2)], 10. T his in turn is oxidized with O-2 to give [[CH2(C5H4)(2)](2)[TiCl](2)(m u-O)], 11. The synthesis of the mononuclear compound [(C5H5CH2C5H4)(C5 H5)TiCl2], 12, is achieved from (C5H5CH2C5H4)Na, 3, and C5H5TiCl3 at l ow temperature in THF. Reduction of 12 with Mg/Hg in the presence of C O yields the Ti(II) complex [(C5H5CH2C5H4)-(C5H5)Ti(CO)(2)], 13.