The reaction of 1,1-diphenylhydrazine with Ti(NMe2)(2)Cl-2 produced the monomeric terminal titanium hydrazido(2-) species Ti(NNPh2)Cl-2(HNMe2)(2) (1) in near-quantitative yield. The reaction of Ti(NMe2)(2)Cl-2 with the less sterically demanding ligand precursors 1,1-dimethylhydrazine or N-aminopiperidine gave the dimeric mu-eta(2),eta(1)-bridged compounds Ti-2(mu-eta(2),eta(1)-NNMe2)(2)Cl-4(HNMe2)(2) (2) and Ti-2{mu-eta(2),eta(1)-NN(CH2)(5)}(2)Cl-4(HNMe2)(3) (3). The X-ray structures of 2 and 3 showed the formation of N-H-... Cl hydrogen bonded dimers or chains, respectively. The reaction of 1 with an excess of pyridine formed [Ti(NNPh2)Cl-2(py)(2)](n) (4, n = 1 or 2). The reaction of the tert-butyl imido complex Ti((NBu)-Bu-t)Cl-2(py)(3) with either 1,1-dimethylhydrazine or N-aminopiperidine again resulted in the formation of hydrazidobridged dimeric complexes, namely Ti-2(mu-eta(2),eta(1)-NNMe2)(2)Cl-4(py)(2) (5, structurally characterized) and Ti{mu-eta(2),eta(1)-NN(CH2)(5)}(2)Cl-4(py)(2) (6). Compounds 1 and 4 are potential new entry points into terminal hydrazido(2-) chemistry of titanium. Compound 1 reacted with neutral fac-N-3 donor ligands to form Ti(NNPh2)Cl-2(Me-3[9]aneN(3)) (7), Ti(NNPh2)Cl-2(Me-3[6]aneN(3)) (8), Ti(NNPh2)Cl-2{HC(Me(2)pz)(3)} (9, structurally characterized), and Ti(NNPh2)Cl-2{HC((n)Bupz)(3)} (10) in good yields (Me-3[9]aneN(3) = trimethyl-1,4,7-triazacyclononane, Me-3[6]aneN(3) = trimethyl-1,3,5-triazacyclohexane, HC(Me(2)pz)(3) = tris(3,5-dimethylpyrazolyl)methane, and HC((n)Bupz)(3) = tris(4-(n)butylpyrazolyl)-methane). DFT calculations were performed on both the model terminal hydrazido compound Ti(NNPh2)Cl-2{HC(pz)(3)} (I) and the corresponding imido compounds Ti(NMe)Cl-2{HC(pz)(3)} (II) and Ti(NPh)Cl-2{HC(pz)(3)} (III). The NNPh2 ligand binds to the metal center in an analogous manner to that of terminal imido ligands (metal equivalent to ligand triple bond), but with one of the Ti=N-alpha pi components significantly destabilized by a pi* interaction with the lone pair of the N-beta atom. The NR ligand sigma donor ability was found to be NMe > NPh > NNPh2, whereas the overall (sigma + pi) donor ability is NMe > NNPh2 > NPh, as judged by fragment orbital populations, Ti-N atom-atom overlap populations, and fragment-charge analysis. DFT calculations on the hydrazido ligand in a a mu-eta(2),eta(1)-bridging mode showed involvement of the N=N pi electrons in donation to one of the Ti centers. This TiN2 interaction is best represented as a metallocycle.