ChemInform Abstract: CATHODIC DIMERIZATION OF FLUOROOLEFINS

Knunyants, I. L.; Rozhkov, I. N.; Stepanov, A. A.; Anitipin, M. Yu.; Kravers, M. A.; Struchkov, Yu. T.

doi:10.1002/chin.198013180

Cited by 1 publication

(7 citation statements)

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“…Our investigations of the reduction of the perfluorinated olefin 5 in THF or DMF confirmed the behavior and potential scale observed by Corvaja et al ( E p5 = −1.1 V vs SCE compared with −1.15 V vs SCE in ref a) for perfluoroolefins' reduction.…”

Section: Resultssupporting

confidence: 91%

“…Its reduction should lead to the expulsion of a second fluoride anion and formation of a CC bond [III]. The CF bond breaking and the electron transfer could be concerted, as for vicinal dihaloalkanes' reduction, 10b-d or successive, as for perfluoralkenes' reduction . There is a priori no evidence for a privileged path.…”

Section: Resultsmentioning

confidence: 99%

“…The general trend observed in the reduction of perfluorinated olefins shows the dependence of the E ° on the branching and number of perfluoroalkyl substituents on the double bond: the more branched, the more positive the E ° of the olefin. , In the case of perfluoralkylphenylcyanides, the unsaturated derivative, obtained by exchange of one electron per carbon atom (reactions I−IV), is expected to be more difficult to reduce than the starting parent and the reduction should stop after an exchange of one electron and a loss of one F - per fluorinated carbon atom.…”

Section: Resultsmentioning

confidence: 99%

“…The following steps ([VIII]−[IX]) were proposed owing to already known reductive behaviors of perfluorinated olefins in organic solvents. , …”

Section: Resultsmentioning

confidence: 99%

“…Since such substrates possess more than one leaving group, the estimation of the number of electrons involved in the first reductive steps was the first difficulty encountered. This question is of importance because reduction of perfluoroalkenes was shown in the literature to occur at rather positive potentials. , …”

Section: Introductionmentioning

confidence: 99%

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Reduction of Polyfluorinated Compounds

2003

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Reduction of perfluoroalkylphenylcyanides and perfluorodecalin was investigated by cyclic voltammetry and interpreted by intramolecular dissociative electron-transfer models, taking into account the dependence of the diffusion coefficient on the molecular volume of the substrate. In both cases, reduction is governed by the first electron transfer and the following chemical reaction corresponding to F- expulsion. In the case of perfluoroalkylphenylcyanides, at the first reduction stage, one electron is exchanged for each fluorinated carbon atom. For perfluorodecalin, the first stage involves a transfer of four electrons, leading to the formation of a diene, in agreement with literature data on the electrochemical behavior of fluorinated olefins. Comparison of the different parameters obtained (standard reduction potentials and cleavage rate constants) with existing thermodynamic values allows us to observe the effect of lowering the C−F bond dissociation energy on the cleavage rate constant when going from primary to tertiary fluorinated carbon atoms. Moreover, deviations from the existing model become more important when the number of electron-withdrawing groups increases, indicating interactions between the radical and fluoride ion fragments. In the special case of perfluorodecalin, the slowness of the electron transfer could be attributed to the nature of the σ* orbital that receives the extra electron.

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Section: Resultssupporting

confidence: 91%