MERGED JET MATRIX ISOLATION STUDIES OF REACTIONS OF CHROMYL CHLORID WITH ORGANIC SUBSTRATES

Abstract

Merged jet deposition in combination with matrix isolation spectroscopy has been employed to study the initial reaction products in the gas phase reactions of $CrCl_{2}O_{2}$ with organic substrates. The merged jet codeposition of $CrCl_{2}O_{2}$ with $CH_{3}OH$ 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 $1425 cm^{-1}$ were identified. Isotopic labeling experiments $(^{13}C, ^{2}H$ and $^{18}O$) suggest that the new absorber contains an intact $CH_{3} O$ group and appears to be bonded to or interacting with one of the oxygens of $CrCl_{2}O_{2}$. 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 $CH_{2} O$ 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 $CO_{2}$. 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.