SYNTHESIS OF VANADIUM AND TITANIUM COMPLEXES OF THE TYPE RM[(ME3SINCH2CH2)3N] (R = CL, ALKYL) AND THE STRUCTURE OF CLV[(ME3SINCH2CH2)3N]

Vanadium and titanium complexes of the type CIM[(Me3SiNCH2CH2)3N] have been synthesized by adding Li3[(Me3SiNCH2)3N] to MCl4L2 (M = Ti, L = THF; M = V, L2 = DME). An X-ray study of ClV[(Me3SiNCH2CH2)3N] (P2(1)/a, a = 15.167 (2) angstrom, b = 10.242 (2) angstrom, c = 16.301 (1) angstrom, beta = 93.705 (8)-degrees, V = 2527 (1) angstrom 3, Z = 4, T = -72-degrees-C, R = 5.8%, R(w) = 5.6%) showed it to be a monomer having pseudo-C3 symmetry. Addition of LiR (M = Ti, R = n-Bu, s-Bu; M = V, LiR = [Li.TMED]CH2SPh) to ClM-[(Me3SiNCH2CH2)3N] gave isolable alkyl derivatives, RM-[(MeSiNCH2CH2)3N]. When it is either heated (70-degrees-C) or treated with H-2 (3 atm, 25-degrees-C), s-BuTi-[(Me3SiNCH2CH2)3N] cleanly cyclometalates via an observable Ti(IV) hydride intermediate (Ti-H delta 8.29).