Distinct reactivities of cis- and trans-RFCF=CFBF2 towards XeF2 and the first synthesis of a [trans-RFCF=CFXe]+ salt

Mendeleev Communications (Impact Factor: 1.15). 05/2007; 17(3):137–138. DOI: 10.1016/j.mencom.2007.05.001
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    ABSTRACT: Data on polyfluorinated organic compounds of boron published in the last decade are generalized. Methods for the synthesis, NMR spectra, and the reactivities of organoboron compounds containing one or several polyfluorinated organic groups at the boron atom are considered.
    Russian Chemical Reviews 11/2010; 79(9):757. · 2.58 Impact Factor
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    ABSTRACT: Bromonium salts [(RF)2Br]Y with perfluorinated groups RFC6F5, CF3CFCF, C2F5CFCF, and CF3C≡C were isolated from reactions of BrF3 with RFBF2 in weakly coordinating solvents (wcs) like CF3CH2CHF2 (PFP) or CF3CH2CF2CH3 (PFB) in 30–90% yields. C6F5BF2 formed independent of the stoichiometry only [(C6F5)2Br][BF4]. 1:2 reactions of BrF3 and silanes C6F5SiY3 (Y=F, Me) ended with different products – C6F5BrF2 or [(C6F5)2Br][SiF5] – as pure individuals, depending on Y and on the reaction temperature (Y=F). With C6F5SiF3 at ≥−30°C [(C6F5)2Br][SiF5] resulted in 92% yield whereas the reaction with less Lewis acidic C6F5SiMe3 only led to C6F5BrF2 (58%). The interaction of K[C6F5BF3] with BrF3 or [BrF2][SbF6] in anhydrous HF gave [(C6F5)2Br][SbF6]. Attempts to obtain a bis(perfluoroalkyl)bromonium salt by reactions of C6F13BF2 with BrF3 or of K[C6F13BF3] with [BrF2][SbF6] failed. The 3:2 reactions of BrF3 with (C6F5)3B in CH2Cl2 gave [(C6F5)2Br][(C6F5)nBF4−n] salts (n=0–3). The mixture of anions could be converted to pure [BF4]− salts by treatment with BF3·base.
    Journal of Fluorine Chemistry 09/2010; 131(9):922-932. · 1.95 Impact Factor
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    ABSTRACT: The replacement of xenon(+) by iodine in reactions of alkenylxenonium(II) salts [RCF=CFXe]Y (R = cis-C2F5, trans-H) and alkynylxenonium(II) salt [C3F7C≡CXe][BF4] with NaI in anhydrous HF (aHF) occurred regiospecifically. At −60 °C the substitution of xenon(+) by bromine in the perfluorinated salts [cis-CF3CF=CFXe]Y and [trans-C4F9CF=CFXe]Y proceeded regio- and stereospecifically with NaBr in aHF, but at a higher temperature and after a longer time the treatment of [cis-C2F5CF=CFXe]Y with NaBr, KBr, or [NBu4]Br in aHF gave mixtures of cisand trans-perfluorobut-1-enyl bromides. The reaction of [C3F7C≡CXe][BF4] with NaBr in aHF at −65 °C gave only 48 %, of C3F7C≡CBr and was accompanied by a mixture of bromine-containing related olefins. Reaction pathways to the main product are discussed.
    Zeitschrift für anorganische Chemie 07/2007; 633(10):1627 - 1632. · 1.25 Impact Factor