- Synthesis and reactivity of perfluoroferracyclocarbenes
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The hydrodimerization of C2 fluoroalkenes to saturated C4 hydrofluorocarbons proceeds via hydrogenolysis of M-C bonds in perfluorometallacyclopentanes. In previous work, hydrogenolysis of Fe[κ2-(CF2)4-](CO)4 (1) was shown to yield expected product H(CF2)4H as well as H2CF(CF2)3H, presumably due to Cα-F bond activation. In this work we investigate ligand-substituted analogs of 1 with regard to their propensity to undergo Cα-F bond activation to give perfluoroferracyclocarbenes. Specifically, reaction of 1 with triphos affords Fe=[CF(CF2)3-](F)(triphos) (5) which reacts further with NaBPh4 in acetonitrile to afford {Fe=[CF(CF2)3-](NCMe)(triphos)}+(BPh4)? (6; triphos = bis(2-diphenylphosphinoethyl)-phenylphosphine). In contrast, reaction of 1 with terpy’ followed by Me3SiOTf gives [Fe=[CF(CF2)3-](terpy’)(CO)]+(OTf)? (9; terpy’ = 4′-(4-methylphenyl)-2,2′:6′,2′′-terpyridine; OTf = SO3CF3). While 5 does not react readily with H2, 6 is readily converted to [FeH(triphos)(NCMe)]+(BPh4)? (10) and H2CF(CF2)3H whereas 9 undergoes a complex reaction with H2, affording HF and a mixture of uncharacterized Fe organofluorine complexes.
- Gabidullin, Bulat M.,Ghostine, Karine,Tom Baker, R.
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- THE FLUORINATION OF BUTANE OVER COBALT TRIFLUORIDE
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The fluorination of butane over cobalt trifluoride has given a complex mixture of partially fluorinated compounds: 51 of these have been identified, comprising over 99percent of the products.Most were polyfluor-butanes but 1-2percent were polyfluoro-2-methylpropanes.The reaction has no synthetic utility.There was some selectivity in the fluorination: secondary C-H was convertart byed into C-F more easily then primary, and the ease of replacement of a particular H was reduced by geminal vicinal fluorines.A computer model of the fluorination was only partially successful, perhaps because the fluorination proceeded in part by simple F for H replacement and in part via alkenes: the model only allowed for the former.
- Burdon, James,Ezmirly, Saleh T.,Huckerby, Thomas N.
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p. 283 - 318
(2007/10/02)
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