The matrix isolation technique and infrared spectroscopy have been used to isolate and characterize for the first time the 1:1 complex of TiCl4 with NH3. Intense spectral features at 440 and 457 cm(-1) were assigned to the Ti-CI antisymmetric stretching modes in this complex; the NH3 symmetric deformation was observed above 1200 cm(-1), shifted over 200 cm(-1) from the parent band position. The spectra suggest a trigonal bipyramidal arrangement about the central titanium with the NH3 ligand in an axial position. A similar set of product bands was observed for the 1:1 complex of TiCl4 with (CH3)(3)N, a species which had been observed previously but not fully characterized. Cryogenic thin film experiments with subsequent warming led to the formation of the 1:1 complex and further reaction products, including the 1:2 complex and two or more amido and/or imido complexes.