Knowledge Bank

Merged jet deposition in combination with matrix isolation spectroscopy has been employed to study the initial reaction products in the gas phase reactions of $CrCl2O2$ with organic substrates. The merged jet codeposition of $CrCl2O2$ with $CH3OH$ into argon matrices led to several reaction products, as a function of the length and temperature of the deposition region. With a merged region (or reaction zone) of 125 cm held at room temperature, new infrared absorptions at 670, 950, 1150 and $1425cm-1$ were identified. Isotopic labeling experiments $(13C,2H$ and $\mathrm{<mrow\; data-mjx-texclass="ORD">18</mrow>}O$) suggest that the new absorber contains an intact $CH3O$ group and appears to be bonded to or interacting with one of the oxygens of $CrCl2O2$. When the merged deposition region was heated above $100\circ C$, these bands were destroyed and strong new bands appeared that could readily be assigned to the known species $CH2O$ and HCl. Further heating (above $200\circ C$) led to reduction and then destruction of these species, and formation of strong bands due to CO and $CO2$. The use of isotopic labels permitted the tracking of the carbon and oxygen atoms of labeled $CH_{3} $OH through the reaction scheme, providing evidence as to the mechanism of this reaction. Very recent experiments have been conducted on the $CrCl_{2}O_{2}/CH_{3} $SH system and will also be described.