Matrix isolation and density functional study of the reaction of OVCl3 with CH3SH

The matrix isolation technique has been combined with infrared spectroscopy to isolate, identify, and characterize the initial intermediates in the th ermal and photochemical reactions of OVCl3 with CH3SH. The thermal reaction proceeds through formation of a 1:1 complex that is characterized by pertu rbations to the -VCl3, -V=O, and S-H stretching modes, as well as the -CH3 rocking and bending modes. The photochemical reaction leads to HCl eliminat ion from the initial 1:1 complex, and formation of Cl2V(O)SCH3. Additional support for the species identification and vibrational band assignments com es from isotopic substitution. Density functional calculations (B3LYP/6-311 G+(d, 2p)) were carried out to confirm the experimental band assignments fo r this latter species. Efforts to study the thermal reaction beyond formati on of the initial complex were unsuccessful, despite pyrolysis at temperatu res as high as 300 degreesC prior to sample deposition.