Synthesis and Characterization of Trifluoromethyl Fluoroformyl Peroxycarbonate, CF<sub>3</sub>OC(O)OOC(O)F

Paci, Maximiliano Alberto Burgos; García, Pablo Andrés; Malanca, Fabio Ernesto; Argüello, Gustavo A.; Willner, Helge

doi:10.1021/ic0261528

Cited by 15 publications

(16 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The vapor pressure of CH 3 OC(O)OOC(O)F within the 233–273 K temperature range follows the equation log p = 8.623–2061/ T ( p /mbar, T /K), and the extrapolated boiling point reaches 366.5 K. It is higher than the one for its fluorinated analogue CF 3 OC(O)OOC(O)F, which boils at 318 K 22. This is an indicator for stronger intermolecular interactions in the condensed phase, which can be rationalized in terms of the difference in dipole moments between both molecules.…”

Section: Resultsmentioning

confidence: 97%

Isolation and Characterization of CH₃OC(O)OOC(O)F from the Reaction CH₃OH + FC(O)OOC(O)F

Berasategui

Paci

Argüello

2011

Zeitschrift anorg allge chemie

Self Cite

View full text Add to dashboard Cite

The synthesis of CH 3 OC(O)OOC(O)F is accomplished by the thermal reaction between CH 3 OH and FC(O)OOC(O)F at room temperature. The new peroxide is obtained in pure form after repeated trap-to-trap condensation and it is characterized by NMR and IR spectroscopy and mass spectrometry. Geometrical parameters were studied by ab initio methods [B3LYP/6-31++G(d,p)]. CH 3 OC(O)OOC(O)F is stable for a few hours at room temperature, and it decomposes into CO

show abstract

Section: Resultsmentioning

confidence: 97%

Isolation and Characterization of CH₃OC(O)OOC(O)F from the Reaction CH₃OH + FC(O)OOC(O)F

Berasategui

Paci

Argüello

2011

Zeitschrift anorg allge chemie

Self Cite

View full text Add to dashboard Cite

show abstract

“…In particular, for the fluorosulfate FS(O 2 )O radical, several experimental and theoretical kinetic investigations have been reported [13][14][15][16][17][18][19][20][21][22]. Interesting compounds could be generated by association reactions between these radicals [23][24][25]. In fact, the FC(O)OOO(O)CF is formed as a byproduct in the thermal reaction between F 2 and CO in the presence of O 2 [26,27].…”

Section: Introductionmentioning

confidence: 99%

Formation and dissociation kinetics of the FC(O)OOO(O)CF, FS(O2)OOO(O2)SF and FC(O)OOO(O2)SF trioxides: A theoretical study

Badenes

Tucceri

Cobos

2014

Chemical Physics Letters

View full text Add to dashboard Cite

“…Our group has extensive experience in the synthesis of fluorocarbooxygenated molecules. − In particular, studies have been carried out on thermal reactions in the gas phase that afforded new species that have been characterized by different techniques and rigorously verified by the kinetic mechanisms proposed. − …”

Section: Introductionmentioning

confidence: 99%

Gas-Phase Reaction between CF₂O and CF₃C(O)OH: Characterization of CF₃C(O)OC(O)F

2019

Self Cite

View full text Add to dashboard Cite

The thermal decomposition of trifluoroacetic acid and carbonyl fluoride (CF 2 O) has been extensively studied because of their importance in the oxidation of hydrochlorofluorocarbons in the atmosphere.We hitherto present the study of the thermal reaction between these two molecules. The reaction mechanism was studied using Fourier transform infrared spectroscopy in the temperature range of 513−573 K. The reaction proceeds homogeneously in the gas phase through the formation of a reaction intermediate, here characterized as CF 3 C(O)OC(O)F (detected for the first time in this work), the major final products being CF 3 C(O)F, HF, and CO 2 .We demonstrate that the reaction is first-order respect to each reagent, second-order global and the mechanism consists of two steps, the first being the rate-determining one. The E a = 110.1 ± 6.1 kJ mol −1 and A = (1.2 ± 0.2) × 10 −12 cm 3 molec −1 s −1 values were obtained from the experimental data. The low activation energy is explained by the hydrogen-bond interactions between the −OH group of the acid and the F atom of the CF 2 O. First-principles calculations at the G4MP2 level of theory were carried out to understand the dynamics of the decomposition. Thermodynamic activation values found for this reaction are as follows: ΔH ⧧ = 105.6 ± 6.4 kJ mol −1 , ΔS ⧧ = −88.6 ± 9.7 J mol −1 K −1 , and ΔG ⧧ = 153.7 ± 13.5 kJ mol −1 . The comparison between theory and experimental results showed excellent similarities, thus strengthening the proposed mechanism.Gangloff et al. 18 studied the thermal decomposition of CF 2 O. The only probable reaction path is the C−F bond scission. The activation energy for this reaction is 323 ± 13 kJ mol −1 . Modica et al. 19 proposed that CF 2 O may react with CO to produce covalent organic framework radicals, but this reaction is completely displaced toward reagents. Ashworth et al. studied the thermal decomposition of CF 3 C(O)OH in the gas phase by Fourier transform infrared (FTIR) spectroscopy, with a stainless steel IR gas cell equipped with silver chloride 49 windows. The main products found for this reaction were 50 CF 3 H and CO 2 . 20 51 The reactions of Cl/F and OH with CF 3 C(O)OH were 52 studied by Wallington and Hurley, 21 concluding that these 53 reactions constitute a minor atmospheric fate of CF 3 C(O)OH 54 and that the major atmospheric removal mechanism would be 55 wet and dry deposition, which probably occurs on a time scale 56 of the order of several weeks. 5,22,23 However, little is known 57 about the reaction of the acid with other stable molecules that 58 have longer lifetimes than the radicals mentioned. 59 Our group has extensive experience in the synthesis of 60 fluorocarbooxygenated molecules. 24−27 In particular, studies 61 have been carried out on thermal reactions in the gas phase 62 that afforded new species that have been characterized by 63 different techniques and rigorously verified by the kinetic 64 mechanisms proposed. 28−30 65 We hereafter present a thorough study of the thermal 66 reaction between CF 3 C(O)OH a...

show abstract

Synthesis and Characterization of Trifluoromethyl Fluoroformyl Peroxycarbonate, CF₃OC(O)OOC(O)F

Cited by 15 publications

References 24 publications

Isolation and Characterization of CH₃OC(O)OOC(O)F from the Reaction CH₃OH + FC(O)OOC(O)F

Isolation and Characterization of CH₃OC(O)OOC(O)F from the Reaction CH₃OH + FC(O)OOC(O)F

Formation and dissociation kinetics of the FC(O)OOO(O)CF, FS(O2)OOO(O2)SF and FC(O)OOO(O2)SF trioxides: A theoretical study

Gas-Phase Reaction between CF₂O and CF₃C(O)OH: Characterization of CF₃C(O)OC(O)F

Contact Info

Product

Resources

About

Synthesis and Characterization of Trifluoromethyl Fluoroformyl Peroxycarbonate, CF3OC(O)OOC(O)F

Cited by 15 publications

References 24 publications

Isolation and Characterization of CH3OC(O)OOC(O)F from the Reaction CH3OH + FC(O)OOC(O)F

Isolation and Characterization of CH3OC(O)OOC(O)F from the Reaction CH3OH + FC(O)OOC(O)F

Formation and dissociation kinetics of the FC(O)OOO(O)CF, FS(O2)OOO(O2)SF and FC(O)OOO(O2)SF trioxides: A theoretical study

Gas-Phase Reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F

Contact Info

Product

Resources

About

Synthesis and Characterization of Trifluoromethyl Fluoroformyl Peroxycarbonate, CF₃OC(O)OOC(O)F

Isolation and Characterization of CH₃OC(O)OOC(O)F from the Reaction CH₃OH + FC(O)OOC(O)F

Isolation and Characterization of CH₃OC(O)OOC(O)F from the Reaction CH₃OH + FC(O)OOC(O)F

Gas-Phase Reaction between CF₂O and CF₃C(O)OH: Characterization of CF₃C(O)OC(O)F