INFRARED SPECTROSCOPIC STUDY OF THE CRYOGENIC THIN-FILM AND MATRIX-ISOLATED COMPLEXES OF TICL4 WITH NH3 AND (CH3)(3)N

The matrix isolation technique and infrared spectroscopy have been use d to isolate and characterize for the first time the 1:1 complex of Ti Cl4 with NH3. Intense spectral features at 440 and 457 cm(-1) were ass igned to the Ti-CI antisymmetric stretching modes in this complex; the NH3 symmetric deformation was observed above 1200 cm(-1), shifted ove r 200 cm(-1) from the parent band position. The spectra suggest a trig onal bipyramidal arrangement about the central titanium with the NH3 l igand in an axial position. A similar set of product bands was observe d for the 1:1 complex of TiCl4 with (CH3)(3)N, a species which had bee n observed previously but not fully characterized. Cryogenic thin film experiments with subsequent warming led to the formation of the 1:1 c omplex and further reaction products, including the 1:2 complex and tw o or more amido and/or imido complexes.