A theoretical study of the decomposition of halogenated alkoxy radicals. II. Fluorine extrusion

Rayez, Jean-Claude; Rayez, Marie-Thérèse; Halvick, Philippe; Duguay, B.; Dannenberg, J. J.

doi:10.1016/0301-0104(87)87042-8

Cited by 14 publications

(16 citation statements)

References 24 publications

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“…The S N 2 reaction leads to the formation of chloride anion Cl − and the dichloromethoxy radical Cl 2 CHO. The radical easily undergoes Cl extrusion, that reaction being rapid when at least 2 chlorine atoms are involved . As for Staneke et al, traces of Cl 2 − are observed in our experiment.…”

Section: Resultssupporting

confidence: 85%

Oxygen anion (O⁻) and hydroxide anion (HO⁻) reactivity with a series of old and new refrigerants

et al. 2018

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The reactivity of a series of commonly used halogenated compounds (trihalomethanes, chlorofluorocarbon, hydrochlorofluorocarbon, fluorocarbons, and hydrofluoroolefin) with hydroxide and oxygen anion is studied in a compact Fourier transform ion cyclotron resonance. O is formed by dissociative electron attachment to N O and HO by a further ion-molecule reaction with ammonia. Kinetic experiments are performed by increasing duration of introduction of the studied molecule at a constant pressure. Hydroxide anion reactions mainly proceed by proton transfer for all the acidic compounds. However, nucleophilic substitution is observed for chlorinated and brominated compounds. For fluorinated compounds, a specific elimination of a neutral fluorinated alkene is observed in our results in parallel with the proton transfer reaction. Oxygen anion reacts rapidly and extensively with all compounds. Main reaction channels result from nucleophilic substitution, proton transfer, and formal H transfer. We highlight the importance of transfer processes (atom or ion) in the intermediate ion-neutral complex, explaining part of the observed reactivity and formed ions. In this paper, we present the first reactivity study of anions with HFO 1234yf. Finally, the potential of O and HO as chemical ionization reagents for trace analysis is discussed.

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Section: Resultssupporting

confidence: 85%

Oxygen anion (O⁻) and hydroxide anion (HO⁻) reactivity with a series of old and new refrigerants

et al. 2018

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“…The extrusion of the fluorine atom adjacent to the oxygen atom is unlikely because these processes are highly endothermic 53.…”

Section: Discussionmentioning

confidence: 99%

Kinetics and mechanism of the thermal gas‐phase oxidation of perfluorobutene‐2 in presence of trifluoromethyl hypofluorite

Romano

Védova

Czarnowski

2003

Int J of Chemical Kinetics

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The oxidation of perfluorobutene-2 (C 4 F 8 ) initiated by trifluoromethyl hypofluorite (CF 3 OF) in presence of O 2 has been studied at 323.1, 332.6, 342.5, and 352.0 K, using a conventional static system. The initial pressure of CF 3 OF was varied between 4.8 and 23.6 Torr, that of C 4 F 8 between 48.7 and 302.4 Torr, and that of O 2 between 51.5 and 270.4 Torr. Several runs were made in presence of 325.5-451.2 Torr of N 2 . The main products were COF 2 , CF 3 C(O)F, and CF 3 OC(O)F. Small amounts of compound containing CF(CF 3 ) O C(O)CF 3 group were also formed, as detected by 13 C NMR spectroscopy. The oxidation is a homogeneous short-chain reaction, attaining, at the pressure of O 2 used, the pseudo-zero-order condition with respect to O 2 as reactant. The reaction is independent of the total pressure. Its basic steps are as follows: the thermal generation of CF 3 O• radicals by the abstraction of fluorine atom of CF 3 OF by

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“…But it can be seen from Figure 1 that, except for the active bond, the lengths of the other bonds are quite similar to the ones of product (HC(O)F). As the respect of TS 2 , TS 3 , the similar characteristics also appear, yet not as notable as TS 1 . Just like what Qiong Luo and Qian Shu Li said, 28 TS 1 can be described as simple H-C bond rupture.…”

mentioning

confidence: 82%

“…As far as we concerned, numerous experiments have been done on methoxy and chloroalkoxy radicals, but few information is available on halogen-substitued alkoxy radical, flouromethoxy, CH 2 FO. [1][2][3][4] Recently, lots of studies indicate that fluoromethoxy and hydroflourocarbon chemistry have become very important in a variety of areas including atmospheric chemistry, combustion suppression, and plasma etching in the microelectronics industries. The investigation of the reactant of CH 2 FO may be of practical value as well as fundamental interest.…”

Section: Introductionmentioning

confidence: 99%

Study on Anharmonic Effect of the Unimolecular Reaction of CH₂(D₂)FO

Zhong¹,

Li²,

Luo³

et al. 2014

Bulletin of the Korean Chemical Society

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Study on the unimolecular reaction for CH2FO and CD2FO is carried out. The structures, energy barriers and zero point energy of the three channels in the title unimolecular reactions are computed with the MP2/6-311++G(3df, 3pd) method. RRKM theory is used to calculate the rate constants of canonical case at temperature range of 500-5000 K and microcanonical system at total energy of 19.05-71.68 kcal/mol. The results indicate that the anharmonic effect and isotope effect are very small for the three channels, and the anharmonic rate constants, around 10 , are close to the experimental prediction reasonably.

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A theoretical study of the decomposition of halogenated alkoxy radicals. II. Fluorine extrusion

Cited by 14 publications

References 24 publications

Oxygen anion (O⁻) and hydroxide anion (HO⁻) reactivity with a series of old and new refrigerants

Oxygen anion (O⁻) and hydroxide anion (HO⁻) reactivity with a series of old and new refrigerants

Kinetics and mechanism of the thermal gas‐phase oxidation of perfluorobutene‐2 in presence of trifluoromethyl hypofluorite

Study on Anharmonic Effect of the Unimolecular Reaction of CH₂(D₂)FO

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A theoretical study of the decomposition of halogenated alkoxy radicals. II. Fluorine extrusion

Cited by 14 publications

References 24 publications

Oxygen anion (O−) and hydroxide anion (HO−) reactivity with a series of old and new refrigerants

Oxygen anion (O−) and hydroxide anion (HO−) reactivity with a series of old and new refrigerants

Kinetics and mechanism of the thermal gas‐phase oxidation of perfluorobutene‐2 in presence of trifluoromethyl hypofluorite

Study on Anharmonic Effect of the Unimolecular Reaction of CH2(D2)FO

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Product

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Oxygen anion (O⁻) and hydroxide anion (HO⁻) reactivity with a series of old and new refrigerants

Oxygen anion (O⁻) and hydroxide anion (HO⁻) reactivity with a series of old and new refrigerants

Study on Anharmonic Effect of the Unimolecular Reaction of CH₂(D₂)FO