NOVEL BIS((TRIMETHYLSILYL)BENZAMIDINATO)TITANIUM(III) COMPLEXES - PREPARATION AND CRYSTAL-STRUCTURES OF (PHC[(ME3SI)N]2)2TI(MU-CL)2LI(TMEDA), (PHC[(ME3SI)N]2)2TI(BH4), AND (PHC[(ME3SI)N]2)2TI(ETA(3)-ALLYL)

The reactions of both TiCl2(TMEDA)2 and TiCl3(THF)3 with 2 equiv of Ph C[(Me3Si)N]2Li(TMEDA) in THF formed forest green crystals of (PhC[(Me3 Si)N]2}2Ti(mu-Cl)2Li(TMEDA) (1) in good yields. Further reaction of 1 in toluene with LiBH4 formed light brown crystals of {PhC[(Me3Si)N]2}2 Ti(BH4) (2). While the reactions of 1 with several organolithium and - magnesium reagents invariably gave intractable residues, a thermally s table Ti(III)-allyl derivative, {PhC [(Me3Si)N] 2}2Ti(eta3-allyl) (4), was obtained in crystalline form from the reaction of 1 with (allyl)M gBr in THF. Crystal data for 1, 2, and 4 are as follows. 1: C32H62N6Si 4Cl2TiLi, M = 768.97, triclinic P1BAR, a = 13.999(9) angstrom, b = 15. 32(1) angstrom, c = 11.279(7) angstrom, alpha = 106.65(5)-degrees, bet a = 96.87(6)-degrees, gamma = 80.43(6)-degrees, V = 2278(3) angstrom3, Z = 2, R = 0.072, R(w) = 0.058, GOF = 4.03, for 366 parameters and 32 17 out of 6379 unique reflections. 2: C26H50N4Si4TiB, M = 589.76, tric linic, P1BAR, a = 12.957(6) angstrom, b = 13.252(5) angstrom, c = 11.4 68(4) angstrom, alpha = 102.24(3)-degrees, beta = 107.53(3)-degrees, g amma = 69.71(3)-degrees, V = 1748(1) angstrom3, Z = 2, R = 0.040, R(w) = 0.046, GOF = 1.53, for 326 parameters and 4604 out of 6156 unique r eflections. 4: C29H51Si4TiN4, M = 615.99, triclinic, P1BAR, a = 11.894 (3) angstrom, b = 15.316(5) angstrom, c = 10.928(2) angstrom, alpha = 101.59(2)-degrees, beta = 93.51(2)-degrees, gamma = 67.16(2)-degrees, V = 1796.8(9) angstrom3, Z = 2, R = 0.043, R(w) = 0.056, GOF = 2.35.