Bis(tetramethylcyclopentadienyl)titanium chemistry. Molecular structures of [(C(5)HMe(4))(mu-eta(1):eta(5)-C(5)Me(4))Ti](2) and [(C(5)HMe(4))(2)Ti]N-2(2)

Thermolysis of bis(tetramethylcyclopentadienyl)-stabilized titanium(III) compounds (C(5)HMe(4))(2)TiR (R = Me (2), Ph (3)) yields, in marked contrast with the bis(pentamethylcyclopentadienyl) analog, the dimeric product [(C(5)HMe(4))(mu-eta(1):eta(5)-C(5)Me(4))Ti](2) (4), With a bridging metalated tetramethylcyclopentadienyl ligand. The hydride (C(5)HMe(4))(2)TiH (5), synthesized by hydrogenolysis of 2 or 3, reacts with N-2 to form the dinuclear Ti(II) dinitrogen compound [(C(5)HMe(4))(2)Ti]N-2(2) (8) Under a dynamic vacuum, the dinitrogen complex 8 loses the N-2 ligand to give the titanocene (C(5)HMe(4))(2)Ti (10). The molecular structures of both 4 and 8 were determined by X-ray diffraction methods.