- Transformations of F-Alkyl Iodides and Bromides Induced by Nickel(0) Carbonyl
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Adducts of primary F-alkyl iodides with nickel carbonyl are formed readily in donor solvents and pyrolyze at 100-150 °C to give olefinic coupling products in high yield. The mechanism proposed to account for the observed chemistry involves preferential α-elimination of fluorine with formation of a carbenoid species complex coordinated to nickel. Differences in reaction paths among several types of substrate halides are rationalized on the basis of polarization of the Ni-C bond in the adducts. Support for these proposals is provided by state-of-the-art calculations.
- Krespan, Carl G.,Dixon, David A.
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- Kinetic and Thermodynamic Studies of the Thermal Electrocyclic Interconversions of Perfluorinated Dienes and Cyclobutenes
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Detailed kinetic and thermodynamic analyses were carried out for the thermal interconversions of (Z,Z)- and (E,E)-perfluoro-2,4-hexadienes with trans-perfluoro-3,4-dimethylcyclobutene, (E,Z)-perfluoro-2,4-hexadiene with perfluoro-cis-3,4-dimethylcyclobutene, (Z,Z)- and (E,E)-perfluoro-3,5-octadienes with trans-perfluoro-3,4-diethylcyclobutene, and (Z)- and (E)-perfluoro-1,3-pentadiene with perfluoro-3-methylcyclobutene.In each case the (Z,Z)- or (Z)-dienes exhibited substantial kinetic advantage over the (E,E)-or (E)-dienes in their cyclization precesses.
- Dolbier, Jr., William R.,Koroniak, Henryk,Burton, Donald J.,Heinze, Pamela L.,Bailey, A.R.,et al.
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p. 219 - 225
(2007/10/02)
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