Infrared Matrix Isolation and Theoretical Study of the Reactions of MoCl4O and MoCl2O2 with CH3OH: Characterization of Cl3Mo(O)OCH3

Abstract

The matrix isolation technique has been employed to investigate the reactions of Cl4MoO and MoCl2O2 with CH3OH and C2H5OH. Using twin jet deposition, the initial intermediate in the mechanism was identified as a weakly bound molecular complex, characterized by perturbations to the MoO and O−H stretching modes. The complex between Cl4MoO and CH3OH was destroyed by near-UV irradiation, producing the novel Cl3Mo(O)OCH3 species and cage-paired HCl. The complex between CH3OH and MoCl2O2 was not photosensitive. Merged jet deposition of CH3OH and Cl4MoO, with a 70 °C reaction zone, led to complete conversion to Cl3Mo(O)OCH3, the same product observed in after irradiation of the 1:1 complex. This species was identified by use of extensive isotopic labeling, by the observation of HCl (or DCl) as an additional reaction product, and by comparison to density functional calculations. Most of the fundamental vibrational modes of this species that lie above 400 cm-1 were observed, some with very high intensities. C2H5OH...