Reaction of [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]TiCl(NMe2)(1) with 1 equiv of PhCH2K, MeMgBr, or Me3SiCH2Li gave corresponding organotitanium alkyl complexes [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(R)(NMe2)(R = CH2Ph (2), CH2-SiMe3 (4), or Me (5)) in good yields. Treatment of 1 with 1 equiv of n-BuLi afforded the decomposition product {[eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti}(2)(mu-NMe)(mu:sigma-CH2NMe) (3). Complex 5 slowly decomposed to generate a mixed-valence dinuclear species {[eta:(5)-sigma Me2C(C5H4)(C2B10H10)]Ti}(2)(mu-NMe2)(mu:sigma-CH2NMe) (6). Complex 1 reacted with 1 equiv of PhNCO or 2,6-Me2C6H3NC to afford the corresponding monoinsertion product [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(Cl)[eta(2)-OC(NMe2)NPh] (7) or [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(Cl)[eta(2)-C(NMe2)=N(2,6-Me2C6H3)] (8). Reaction of 4 or 5 with 1 equiv of R'NC gave the titanium eta(2)-iminoacyl complexes [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(NMe2)[eta C-2(R) = N(R')] (R = CH2SiMe3, R' = 2,6- Me2C6H3 (9) or Bu-t (10); R = Me, R' = 2,6-Me2C6H3 (11) or Bu-t (12)). The results indicated that the unsaturated molecules inserted into the Ti - N bond only in the absence of the Ti C( alkyl) bond and that the Ti - C( cage) bond remained intact. All complexes were fully characterized by various spectroscopic techniques and elemental analyses. Molecular structures of 2, 3, 6 - 8, and 10 -12 were further confirmed by single-crystal X-ray analyses.