Reaction of (RCsH4)TiClj (la, R = H; lb, R = CH3) with Li(NH(t-Bu)} in THF affords (RCsH4)TiC12{NH(r-Bu)) (2a, R = H; 2b, R = CH3) in 80-90% isolated yields. The moisture-sensitive red-orangecompoundscan becrystallized from CHzClJhexane mixtures. The X-ray structures for the two compounds were determined and found to be similar. Multiple-bond character in the Ti-N bond is suggested by short Ti-N distances, 1.879 (3) A (2a) and 1.871 (5) A (2b). Data were collected on an Enraf-Nonius CAD-4 diffractometer (X(Mo Ka) = 0.710 73 A) in the -28 mode to a maximum 28 of 52'. Crystal data for 2a: C~H I S C~~N T~, M r = 256.03, monoclinic, P21/m, a = 6.149 (1) A, b = 10.888 (3) A, c = 9.004 (3) A, / 3 = 100.44 (2)O, V = 593 A3, Dcald = 1.43 g ~m -~, Z = 2. A total of 1352 reflections were collected, of which 1239 were unique, and 836 reflections with Fo2 > 3.0u(F0)2 were used in the refinement, which gave R = 0.036 and R, = 0.045. Crystal data for 2b: C I O H I~C~Z N T~, M, = 270.06, monoclinic, P21/c, o = 6.198 (2) A, b = 11.660 (2) A, c = 17.748 (4) A, 6 = 98.73 (2)', V = 1268 A3, Dcald = 1.41 g cm-3,Z = 4. A total of 2865 reflections were collected, of which 2620 were unique, and 990 reflections with F2> ~.OU(F,)~ were used in the refinement, which gave R = 0.048 and R, = 0.051. A variable-temperature NMR study was conducted to further explore the r-character of the Ti-N bond.