The deposition of titanium nitride films from single-source precursors bearing alkylhydrazine-derived ligands is reported. The complex [Ti 2Cl 4(NN(CH 3) 2) 2(NH 2N(CH 3) 2) 2] sublimes at 140–150°C (0.1 mmHg) and affords titanium nitride films in a chemical vapor deposition reactor at substrate temperatures of ⩾400°C. By contrast, structurally related single-source precursors containing alkylamine- or ammonia-derived ligands deposit titanium (IV) nitride chloride films at 400°C in the same reactor, and only afford titanium nitride films at ⩾475°C. The hydrazide(1−) complex [TiCl 2(N(CH 3)N(CH 3) 2) 2] sublimes at 130°C (0.1 mmHg) and affords titanium nitride films at 600°C. At substrate temperatures of ⩽550°C, poorly adherent blue-colored coatings were obtained. The atmospheric pressure chemical vapor deposition reaction of titanium tetrachloride and 1,1-dimethylhydrazine affords titanium nitride films at >500°C, but gives titanium (IV) nitride chloride films at ⩽500°C. Characterization of the films obtained from the depositions is described. The results demonstrate that ligands derived from 1,1-dialkylhydrazines can be powerful reducing sources for high valent early transition metals, depending on the ligand coordination mode, and can lead to a significant reduction in deposition temperatures compared to traditional nitrogen sources in cases where a high valent metal source compound must be reduced to a lower oxidation state.