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A Systematic Investigation into the Mechanism of the Reaction Between CF 3 Radicals and CO/O 2
Author(s) -
Burgos Paci Maximiliano A.,
Argüello Gustavo A.
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305480
Subject(s) - isotopomers , radical , chemistry , yield (engineering) , reaction mechanism , peroxide , fourier transform infrared spectroscopy , reaction intermediate , reagent , spectroscopy , computational chemistry , organic chemistry , catalysis , molecule , materials science , physics , quantum mechanics , metallurgy
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 3 OC(O)OOOC(O)OCF 3 , and of the stable peroxide, CF 3 OC(O)OOC(O)OCF 3 . Analyses were carried out by means of FTIR spectroscopy in combination with ab initio calculations. At temperatures close to 0 °C, 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.