MATRIX-ISOLATION STUDY OF THE 1 1-COMPLEXES OF TICL4 WITH SULFUR-CONTAINING BASES/

The matrix isolation technique has been employed to isolated intermedi ate 1:1 molecular complexes of TiC1(4) with H2S, CB3SH and (CH3)(2)S. Each complex was subsequently characterized by infrared spectroscopy, and distinctive vibrational modes characteristic of complex formation were identified. These include two Ti-Cl stretching modes at low energ y, and one or more vibrational modes of the coordinated base. In addit ion, hydrogen bonded complexes of each of these bases with HCl were ob served, due to the presence of residual HCl in samples of TiCl4. Merge d jet copyrolysis experiments were then conducted far each pair of rea gents. In contrast to the analogous oxygen bases, no new intermediates were observed with pyrolysis temperatures as high at 375 degrees C, a lthough indirect evidence of further reaction was obtained. (C) 1997 E lsevier Science B.V.