Matrix isolation and density functional study of the reactions of OVCl3 with CH3OH: Synthesis and characterization of Cl2V(O)OCH3

The matrix isolation technique has been employed to investigate the reactio n of OVCl3 with CH3OH. Using twin jet deposition, the initial intermediate in the mechanism was identified as a weakly bound molecular complex. This s pecies is characterized by perturbations to the C-O, V=O, and V-Cl stretchi ng modes. Merged jet deposition, with a room-temperature reaction zone, led to complete conversion to Cl2V(O)OCH3, the second intermediate in the reac tion sequence, through HCl elimination from the initial complex. This speci es was identified by use of extensive isotopic labeling, the observation of HCl as an additional reaction product, and by comparison to density functi onal calculations. All of the fundamental vibrational modes of this species that lie above 400 cm(-1) were observed, some with very high intensities. Heating the reaction zone above 150 degrees C led to destruction of this in termediate, and production of both CH2O and CH3Cl.