The Trifluoromethoxycarbonyl Radical CF3OCO

Ahsen, Stefan von; Hufen, Julia; Willner, Helge; Francisco, Joseph S.

doi:10.1002/1521-3765(20020301)8:5<1189::aid-chem1189>3.0.co;2-j

Cited by 28 publications

(31 citation statements)

References 29 publications

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“…The CF 3 O group behaves in several cases as a pseudo-fluorine atom. [28] The Gaussian band profile is found in the UV spectra of the three radicals CF 3 [32] offers the CIS-method [37] to calculate energies for the transition from a molecule×s ground state to excited states. The absolute energy values show large deviations from the experimental data, but the described trend in the series CF 3 OO, FC(O)OO, and CF 3 OC(O)OO is reproduced well by the calculations.…”

Section: Resultsmentioning

confidence: 65%

“…The only observed product was the adduct CF 3 O ¥ O 2 , which is subject of a further study. [31] This result indicates a reaction between CF 3 O and O 2 that is much faster than the reaction of CF 3 O with CO. In the gas phase under laboratory or atmospheric conditions CF 3 OCO should have similar behavior to FCO radicals, which add molecular oxygen rapidly.…”

Section: Resultsmentioning

confidence: 99%

“…[27] The modified synthesis of CF 3 OC(O)OOC(O)-OCF 3 , [26] at À 40 8C instead of 0 8C yields the corresponding trioxide CF 3 OC(O)OOOC(O)OCF 3 as main product. [27] The proposed scheme [26,28] for this reaction includes the radicals CF 3 OCO and CF 3 OC(O)OO. The former species CF 3 OCO was the subject of a recent matrix isolation study, [28] which is now extended in this paper to the elusive CF 3 OC(O)OO radical.…”

Section: Introductionmentioning

confidence: 99%

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The Trifluoromethoxy Carbonyl Peroxy Radical CF3OC(O)OO

Ahsen¹,

Willner²,

Francisco

2002

Chem. Eur. J.

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Section: Resultsmentioning

confidence: 65%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The Trifluoromethoxy Carbonyl Peroxy Radical CF3OC(O)OO

Ahsen¹,

Willner²,

Francisco

2002

Chem. Eur. J.

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“…If the bonds within both fragments A and B are stronger than the A-B bond of the precursor, little secondary bond cleavage of the A or B radicals should occur. These conditions were found for several typical experiments that we performed in recent years, not only in the case of fluorocarbon radical formation [35,36,38], but also in the synthesis of new chlorine oxide radicals [39][40][41]. An early example was the thermal fragmentation of peroxyacetyl nitrate (PAN) which has led to new spectroscopic data of the peroxyacetyl radical [42]:…”

Section: Formation Of Fluorocarbon Oxy and Peroxy Radicals In The Labmentioning

confidence: 99%

Fluorocarbon oxy and peroxy radicals

Ahsen¹,

Willner²,

Argüello

2004

Journal of Fluorine Chemistry

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“…The reactive intermediates bis(trifluoromethyl)peroxy dicarbonate, CF 3 OC(O)OOC(O)OCF 3 have been studied by NMR, vibration, and UV spectroscopy [10] . Recently, the geometry structure [11] (Figure 2) and pyrolysis [21] have also been reported. By using a homemade ultraviolet photoelectron spectrometer-photoionization mass spectrometer (PES-PIMS), we investigated the photochemical reaction of CF 3 radicals with CO and O 2 .…”

Section: Resultsmentioning

confidence: 99%

Study on the atmospheric photochemical reaction of CF3 radicals using ultraviolet photoelectron and photoionization mass spectrometer

Yao

Yin

et al. 2008

Sci. China Ser. B-Chem.

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A study of the atmospheric photochemical reaction of CF 3 radical with CO and O 2 was performed by using a homemade ultraviolet photoelectron spectrometer-photoionization mass spectrometer (PES-PIMS). The electronic structures and mechanism of ionization and dissociation of CF 3 OC(O)OOC(O)-OCF 3 were investigated. It was indicated that the two bands on the photoelectron spectrum of CF 3 OC(O)OOC(O)OCF3 are the result of ionization of an electron from a lone pair of oxygen and a fluorine lone pair of CF 3 group. The outermost electrons reside in the oxygen lone pair. The experimental and theoretical first vertical ionization energy is 13.21 and 13.178 eV, respectively, with the PES and OVGF method. They are in good agreement. The photo ionization and dissociation processes were discussed with the help of theoretical calculations and PES-PIMS experiment. After ionization, the parent ions prefer the dissociation of the C-O bond and giving the fragments CF 3 OCO + and CF3 + . It demonstrated that the ultraviolet photoelectron and photoionization mass spectrometer could be applied widely in the study of atmospheric photochemical reaction. photochemical reaction, CF 3 radical, ultraviolet photoelectron and photoionization mass spectroscopy, transient speciesIt is now well established that the chlorofluorocarbons (CFCs) are responsible for the catalytic destruction of the ozone in the atmosphere and global warming [1] . As substitutes for one class of these stable compounds, various hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) are presently being considered. Their degradation takes place in the troposphere through a series of photochemical reactions [2] . At present, it is important to study the mechanism, intermediate, and products in the process of the degradation of HCFCs and HFCs [3,4] . Ultraviolet photoelectron spectroscopy (UPS) is an important method to study gaseous transient species [5,6] . To improve our ability on studying transient species, our group has built up a photoelectron spectrometer-photoionization mass spectrometer (PES-PIMS) [7] . The modification of the spectrometer was based on the HeI photoelectron spectrometer. Using this new apparatus, we can not only obtain a direct measure of electronic structure and energy levels of stable and unstable molecules, but also provide the information on the complicated process of reaction, ionization, and dissociation [8,9] .In this work, we combined a newly-made on-line photochemical reactions apparatus to our homemade PES-PIMS, and studied the application of this new apparatus in the study on the photochemical reactions of CF 3 radicals with CO and O 2 . With the help of quantum chemical calculation, we investigated the electronic

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The Trifluoromethoxycarbonyl Radical CF3OCO

Cited by 28 publications

References 29 publications

The Trifluoromethoxy Carbonyl Peroxy Radical CF3OC(O)OO

The Trifluoromethoxy Carbonyl Peroxy Radical CF3OC(O)OO

Fluorocarbon oxy and peroxy radicals

Study on the atmospheric photochemical reaction of CF3 radicals using ultraviolet photoelectron and photoionization mass spectrometer

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