1031690-99-9Relevant academic research and scientific papers
Fluorine for hydrogen exchange in the hydrofluorobenzene derivatives C 6HxF(6-x), where x = 2, 3, 4 and 5 by monomeric [1,2,4-(Me3C)3C5H2]2CeH: The solid state isomerization of [1,2,4-(Me3C)3C 5H2]2Ce(2,3,4,5-C6HF4) ...
Werkema, Evan L.,Andersen, Richard A.
, p. 7153 - 7165 (2008/12/22)
Full title: Fluorine for hydrogen exchange in the hydrofluorobenzene derivatives C 6HxF(6-x), where x = 2, 3, 4 and 5 by monomeric [1,2,4-(Me3C)3C5H2]2CeH: The solid state isomerization of [1,2,4-(Me3C)3C 5H2]2Ce(2,3,4,5-C6HF4) to [1,2,4-(Me3C)3C5H2] 2Ce(2,3,4,6-C6HF4). The reaction between monomeric bis(1,2,4-tri-tert-butylcyclopentadienyl) cerium hydride, Cp′2CeH, and several hydrofluorobenzene derivatives is described. The aryl derivatives that are the primary products, Cp′2Ce(C6H5-xFx) where x = 1,2,3,4, are thermally stable enough to be isolated in only two cases, since all of them decompose at different rates to Cp′2CeF and a fluorobenzyne; the latter is trapped by either solvent when C6D 6 is used or by a Cp′H ring when C6D12 is the solvent. The trapped products are identified by GC/MS analysis after hydrolysis. The aryl derivatives are generated cleanly by reaction of the metallacycle, Cp′((Me3C)2C5H 2C(Me2)CH2)Ce, with a hydrofluorobenzene, and the resulting arylcerium products, in each case, are identified by their 1H and 19F NMR spectra at 20°C. The stereochemical principle that evolves from these studies is that the thermodynamic isomer is the one in which the CeC bond is flanked by two ortho-CF bonds. This orientation is suggested to arise from the negative charge that is localized on the ipso-carbon atom due to Co(δ+)Fo(δ-) polarization. The preferred regioisomer is determined by thermodynamic rather than kinetic effects; this is illustrated by the quantitative, irreversible solid-state conversion at 25°C over two months of Cp′2Ce(2, 3,4,5-C6HF4) to Cp′2Ce(2,3,4,6-C 6HF4), an isomerization that involves a CeC(ipso) for C(ortho)F site exchange.
