SYNTHESIS AND CHARACTERIZATION OF NOVEL TITANIUM(III) AND TITANIUM-(IV) ALKYLS AND CARBENES SUPPORTED BY AMIDE LIGANDS - CRYSTAL-STRUCTURE OF [(CY(2)N)(2)TI(MU-CH2)](2)

Reaction of (Cy(2)N)(2)Ti(mu-Cl)(2)Li(TMEDA) (1) [TMEDA = N,N,N',N'-te tramethylethylene-diamine] with MeLi formed different complexes depend ing on the stoichiometric ratio of the reactants used. The novel Ti(II I) complex (Cy(2)N)(2)Ti(mu-Me)(2)Li(TMEDA) (2) was formed when 2 equi v of the organolithium reagent was used, while a tetravalent complex, (Cy(2)N)(2)-TiMe(2) (3), was formed when a stiochiometric ratio of 1:1 was used. Complex 3 rapidly decomposed in toluene at 60 degrees C to form the bridging methylene complex (Cy(2)N)(2)Ti(mu-CH2)(2)-Ti(NCy(2) )(2) (5). The structures of 2, 3, and 5 were elucidated by X-ray diffr action analysis. Crystal data are as follows. 2: C32H66N4TiLi, M = 561 .74, monoclinic, P2(1)/n, a 12.505(5) Angstrom, b = 19.333(9) Angstrom , c = 15.393(5) Angstrom, beta = 109.10(2)degrees, V = 3517(3) Angstro m(3), Z = 4, T = -160 degrees C, Mo K alpha, R = 0.066, R(w) = 0.061 f or 3644 reflections and 343 parameters. Non-hydrogen atoms were refine d anisotropically. 3: C26H50N2Ti, M = 438.59, monoclinic, P2(1)/n, a = 9.906(4) Angstrom, b = 18.520(6) Angstrom, c = 14.271(4) Angstrom, be ta = 96.87(3)degrees, V = 2599(3) Angstrom(3), Z = 4, T = -161 degrees C, Mo K alpha, R = 0.053, R(w) = 0.065 for 3132 reflections and 263 p arameters. Non-hydrogen atoms were refined anisotropically. 5: C50H92N 2Ti2, M = 845.10, monoclinic, P2/n, a = 13.6190(9) Angstrom, b = 12.48 4(1) Angstrom, c 14.811(1) Angstrom, beta = 96.510(3)degrees, V 2501.9 (6) Angstrom(3), Z = 2, T = -160 degrees C, Mo K alpha, R = 0.057, R(w ) = 0.065 for 2637 reflections and 343 parameters. Non-hydrogen atoms were refined anisotropically.