406-82-6Relevant articles and documents
Fluorine substitution effects on the alkyl coupling reaction on a Ag(111) surface
Paul, Anumita,Gellman, Andrew J.
, p. 9056 - 9066 (2007/10/03)
We have investigated fluorine substitution effects on the rate of coupling of adsorbed alkyl groups on a Ag(111) surface. Alkyl groups are formed by thermal dissociation of the C-I bond in adsorbed alkyl iodides. Variable heating rate temperature programmed reaction (TPR) studies were used to determine the kinetic parameters for the coupling of ethyl groups and propyl groups. They are Ea = 15.1 ± 0.6 kcal/mol, v = 1016.7±0.8 s-1 and Ea = 16.9 ± 0.4 kcal/mol, v = 1017.1±0.4 s-1, respectively. Substitution of fluorine for hydrogen in the adsorbed alkyl groups systematically raises the coupling reaction temperature. For example, trifluoropropyl groups self-couple at temperatures ~70 K higher than propyl groups on Ag(111). Coadsorbed propyl and trifluoropropyl groups cross-couple at temperatures ~10 K higher than the propyl self-coupling reaction. The kinetic parameters evaluated from the results of this study and from results of earlier studies by X.-L. Zhou, J. M. White, and co-workers [Surf. Sci. 1989, 219, 294; Catal. Lett. 1989, 2, 375; J. Phys. Chem. 1991, 95, 5575] are used to plot linear free energy relationships (LFER) which provide insight into the electronic nature of the reaction center. The implication of the LFER plots for the surface alkyl coupling reaction is that the reaction center in the transition state is electron deficient with respect to the initial state.
Addition of Free Radicals to Unsaturated Systems. Part 23. Photochemical and Thermal Reactions of Trifluoroiodomethane with But-2-ene and But-1-ene
Davies, Terry,Haszeldine, Robert N.,Tipping, Anthony E.
, p. 927 - 932 (2007/10/02)
Photochemically-initiated addition of trifluoroiodomethane to but-2-ene gives as the major product the 1:1 adduct 2-iodo-3-trifluoromethylbutane as a mixture of the erythro- and threo-isomers together with compounds formed via dehydroiodination of the 1:1 adduct.Reduction of the 1:1 adduct to 2-trifluoromethylbutane is a major process when the reaction tube is shaken.Under thermal conditions fewer products arising via dehydroiodination of the 1:1 adduct are detected, but products formed via isomerisation of the reactant olefin to but-1-ene are present in low yield.With but- 1-ene initial bidirectional CF3 radical attack takes place to give the 1:1 adducts 1,1,1-trifluoro-3-iodopentane and 1-iodo-2-trifluoromethylbutane in the ratio ca. 19:1.Products are also formed via isomerisation of the reactant olefin and via dehydroiodination of the 1:1 adducts.