Infrared matrix isolation spectra of some perfluoro organic free radicals. 2. CF3O2

IR and UV Spectra of the Matrix‐Isolated Peroxy Radicals CF3OO,trans‐FC(O)OO, andcis‐FC(O)OO

“…Therefore, we have unambiguously identified eleven of the twelve fundamentals of CF 3 OO, two more than previously known. In addition, the results of the first excellent matrix study on CF 3 OO [20] are confirmed; however, five of the earlier assignments are revised (n 2 D n 9 ; n 6 D n 10 ; n 11 3 n 8 ). The IR spectra of cis-and trans-FC(O)OO: A typical IR spectrum of the pyrolysis products of FC(O)OONO 2 , which contains a mixture of cis-and trans-FC(O)OO radicals, is shown in Figure 2.…”

“…[18,19] The IR spectrum of CF 3 OO was obtained from several matrix studies. [20±23] Butler and Snelson produced CF 3 OO by vacuum pyrolysis of CF 3 I followed by co-condensation with oxygen-doped argon at 12 K. [20] Most of the results were confirmed by photooxidation experiments of CF 3 I/O 2 in an argon matrix. [21±23] To our knowledge, no experimental IR data of FC(O)OO have been published to date.…”

The Trifluoromethoxy Carbonyl Peroxy Radical CF3OC(O)OO

“…Because in the heated zone the partial pressure of the trioxide is about 10 À3 mbar and the residence time of the trioxide/noble gas mixtures is about 10 À3 s, mainly monomolecular reactions occur and the weakest bond is broken according to Equation (6) [reaction enthalpy of the reaction in Eq. (6) amounts 65.1 kJ mol À1 , calculated with B3LYP method and 6-311G(d,p) basis set]:…”

“…All unidentified IR bands disappeared simultaneously, while the bands of CF 3 O showed a slower decay due to its comparable small absorption cross sections for the light used. [29] CF 3 OO [6,10] was identified as a photolysis product, together with CO 2 and COF 2 . When using UV light with wavelength shorter than 254 nm, the photochemically generated CF 3 OO is also partially photolyzed.…”

Fluorocarbon oxy and peroxy radicals

“…However, the matrix isolation techniques offer the possibility of producing radicals in high yield and only milligram quantities of the precursors are needed. The desired radicals can be produced either by low pressure flash thermolysis of suitable precursors with subsequent matrix isolation of the products, by codeposition of radicals with reactive matrix materials or by photolysis of matrix isolated species [31][32][33][34][35][36]. In a matrixisolation experiment, a high vacuum and the use of highly diluted precursor molecules during matrix deposition offer the appropriate conditions for the synthesis of short-lived radicals by low pressure flash thermolysis [37].…”