Matrix isolation infrared spectroscopic and density functional study of the mechanism of the oxidation of CH3OH by CrCl2O2

Article abstract of DOI:10.1021/ja9808752

The matrix isolation technique has been employed to isolate several intermediates, in sequence, in the oxidation of CH₃OH by CrCl₂O₂. Consistent with previous theoretical calculations, a hydrogen-bonded complex formed initially after twin jet deposition and was enhanced by matrix annealing to 33 K. This complex was photodestroyed by Hg are irradiation with λ < 500 nm, and led to the production of HCl and ClCrO₂OCH₃. These species were also produced by room temperature reaction of the two precursors in a flow system followed by rapid matrix trapping. Heating the flow reaction zone above 150°C led to destruction of ClCrO₂OCH₃, and production of CH₂O and HCl. Above 250°C bands due to CH₂O were destroyed and bands due to CO and CO₂ grew in. High-level density functional calculations (B3LYP/6-311G*) were carried out to identify potential intermediates in this system and to provide theoretical vibrational spectra for comparison to experiment.