A Systematic Investigation into the Mechanism of the Reaction Between CF_3 Radicals and CO/O_2

摘要

A complete study of the reaction of CF_3 radicals in the presence of CO and O_2 was carried out by using isotopically labeled reagents to form, selectively, all the possible isotopomers of the intermediate trioxide, CF_3OC(O)OOOC(O)OCF_3, and of the stable peroxide, CF_3OC(O)OOC(O)OCF_3. Analyses were carried out by means of FTIR spectroscopy in combination with ab initio calculations. At temperatures close to 0degC, the acyloxy radicals formed were shown to exist long enough to yield a statistical mixture of isotopomers. In previous reports their lifetime was considered to be too short.