Several titanium(III) complexes incorporating the chelating diamidoamine ligand [Me3SiNCH2CH2)(2)NSiMe3](2-)[NN2] are described. The reaction between Li-2[NN2] and TiCl3(THF)(3)(THF = tetrahydrofuran) resulted in the formation of the dimeric titanium(III) chloride {TiCl[NN2]}(2) 1, from which the monomeric titanium(III) alkyl Ti{CH(SiMe3)(2)}[NN2] 2 could be synthesized via a salt metathesis route. The alkyl complex 2 was found to react with hydrogen gas to form the thermally stable; dimeric, diamagnetic titanium(III) hydride {TiH[NN2]}(2) 3; density functional calculations on a simplified model system of 3 indicated the presence of a weak Ti-Ti sigma-interaction. The solid-state structures of 1, 2, and 3 are described.