- (Fluoroorgano)fluoroboranes and -fluoroborates: Part 3. Polyfluoroalken-1-yldifluoroboranes
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Polyfluoroalken-1-yldifluoroboranes RCF=CFBF2 (R=F, cis-, trans-Cl, trans-C4F9, cis-C2F5, cis-C6F13, trans-C4H9, trans-C6H5) were prep
- Frohn,Bardin
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- Organocatalytic C?F Bond Activation with Alanes
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Hydrodefluorination reactions (HDF) of per- and polyfluorinated olefins and arenes by cheap aluminum alkyl hydrides in non-coordinating solvents can be catalyzed by O and N donors. TONs with respect to the organocatalysts of up to 87 have been observed. Depending on substrate and concentration, high selectivities can be achieved. For the prototypical hexafluoropropene, however, low selectivities are observed (E/Z≈2). DFT studies show that the preferred HDF mechanism for this substrate in the presence of donor solvents proceeds from the dimer Me4Al2(μ-H)2?THF by nucleophilic vinylic substitution (SNV)-like transition states with low selectivity and without formation of an intermediate, not via hydrometallation or σ-bond metathesis. In the absence of donor solvents, hydrometallation is preferred but this is associated with inaccessibly high activation barriers at low temperatures. Donor solvents activate the aluminum hydride bond, lower the barrier for HDF significantly, and switch the product preference from Z to E. The exact nature of the donor has only a minimal influence on the selectivity at low concentrations, as the donor is located far away from the active center in the transition states. The mechanism changes at higher donor concentrations and proceeds from Me2AlH?THF via SNV and formation of a stable intermediate, from which elimination is unselective, which results in a loss of selectivity.
- Jaeger, Alma D.,Ehm, Christian,Lentz, Dieter
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supporting information
p. 6769 - 6777
(2018/04/02)
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- Unimolecular reactions in the CF3CH2Cl ? CF 2ClCH2F system: Isomerization by interchange of Cl and F atoms
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The recombination of CF2Cl and CH2F radicals was used to prepare CF2ClCH2F* molecules with 93 ± 2 kcal mol-1 of vibrational energy in a room temperature bath gas. The observed unimolecular reactions in order of relative importance were: (1) 1,2-ClH elimination to give CF2=CHF, (2) isomerization to CF 3CH2Cl by the interchange of F and Cl atoms and (3) 1,2-FH elimination to give E- and Z-CFCl=CHF. Since the isomerization reaction is 12 kcal mol-1 exothermic, the CF3CH2Cl* molecules have 105 kcal mol-1 of internal energy and they can eliminate HF to give CF2=CHCl, decompose by rupture of the C-Cl bond, or isomerize back to CF2ClCH2F. These data, which provide experimental rate constants, are combined with previously published results for chemically activated CF3CH2Cl* formed by the recombination of CF3 and CH2Cl radicals to provide a comprehensive view of the CF3CH2Cl* ? CF 2ClCH2F* unimolecular reaction system. The experimental rate constants are matched to calculated statistical rate constants to assign threshold energies for the observed reactions. The models for the molecules and transition states needed for the rate constant calculations were obtained from electronic structures calculated from density functional theory. The previously proposed explanation for the formation of CF2=CHF in thermal and infrared multiphoton excitation studies of CF3CH 2Cl, which was 2,2-HCl elimination from CF3CH 2Cl followed by migration of the F atom in CF3CH, should be replaced by the Cl/F interchange reaction followed by a conventional 1,2-ClH elimination from CF2ClCH2F. The unimolecular reactions are augmented by free-radical chemistry initiated by reactions of Cl and F atoms in the thermal decomposition of CF3CH2Cl and CF 2ClCH2F.
- Enstice, Erin C.,Duncan, Juliana R.,Setser,Holmes, Bert E.
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experimental part
p. 1054 - 1062
(2011/04/18)
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