Bs. Ault, MATRIX-ISOLATION INFRARED SPECTROSCOPIC AND DENSITY-FUNCTIONAL STUDY OF THE MECHANISM OF THE OXIDATION OF CH3OH BY CRCL2O2, Journal of the American Chemical Society, 120(24), 1998, pp. 6105-6112
The matrix isolation technique has been employed to isolate several in
termediates, in sequence, in the oxidation of CH3OH by CrCl2O2. Consis
tent 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 irradiat
ion with lambda < 500 nm, and led to the production of HCl and ClCrO2O
CH3. 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 degrees C led to destruction
of ClCrO2OCH3, and production of CH2O and HCl. Above 250 degrees C ba
nds due to CH2O were destroyed and bands due to CO and CO2 grew in. Hi
gh-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.