29646-16-0Relevant articles and documents
Facile and systematic access to the least-coordinating WCA [(RFO)3Al-F-Al(ORF)3]- and its more Lewis-basic brother [F-Al(ORF)3]- (RF = C(CF3)3)
Martens, Arthur,Weis, Philippe,Krummer, Michael Christian,Kreuzer, Marvin,Meierh?fer, Andreas,Meier, Stefan C.,Bohnenberger, Jan,Scherer, Harald,Riddlestone, Ian,Krossing, Ingo
, p. 7058 - 7068 (2018)
By reaction of the Lewis acid Me3Si-F-Al(ORF)3 with a series of [PF6]- salts, gaseous PF5 and Me3Si-F are liberated and salts of the anion [F-Al(ORF)3]- ([f-al]-; RF = C(CF3)3) can be obtained. By addition of another equivalent of Me3Si-F-Al(ORF)3 to [f-al]-, gaseous Me3Si-F is released and salts of the least coordinating anion [(RFO)3Al-F-Al(ORF)3]- ([al-f-al]-) are formed. Both procedures work for a series of synthetically useful cations including Ag+, [NO]+, [Ph3C]+ and in very clean reactions with 5 g batch sizes giving excellent yields typically exceeding 90%. In addition, the synthesis of Me3Si-F-Al(ORF)3 has been optimized and scaled up to 85 g batches in an one-pot procedure. These anions could previously only be obtained by difficult to control decomposition reactions of [Al(ORF)4]- or by halide abstraction reactions with Me3Si-F-Al(ORF)3, generating relatively large countercations that are unsuited for further use as universal starting materials. Especially [al-f-al]- is of interest for the stabilization of reactive cations, since it is even weaker coordinating than [Al(ORF)4]- and more stable against strong electrophiles. This bridged anion can be seen as an adduct of [f-al]- and Al(ORF)3. Thus, it is similarly Lewis acidic as BF3 and eventually reacts with nucleophiles (Nu) from the reaction environment to yield Nu-Al(ORF)3 and [f-al]-. This prevents working with [al-f-al]- salts in ethereal or other donor solvents. By contrast, the [f-al]- anion is no longer Lewis acidic and may therefore be used for reactions involving stronger nucleophiles than the [al-f-al]- anion can withstand. Subsequently it may be transformed into the [al-f-al]- salt by simple addition of one equivalent of Me3Si-F-Al(ORF)3.
Syntheses of "phosphine-Free" Molybdenum Oxo Alkylidene Complexes through Addition of Water to Alkylidyne Complexes
Zhai, Feng,Schrock, Richard R.,Hoveyda, Amir H.,Müller, Peter
, p. 2486 - 2492 (2020)
Addition of 1 equiv of water to Mo(CArp)(ORF9)3 (Arp = p-methoxyphenyl; ORF9 = OC(CF3)3) in the presence of 5percent NEt3 (vs Mo) in THF led to the formation of Mo(O)(CHArp)(ORF9)2(THF)2 in good yield. Mo(O)(CHArp)(ORF9)2(THF)2 reacts with 2 equiv of LiOH
PERFLUORINATED ALLYL ETHERS AND PERFLUORINATED ALLYL AMINES AND METHODS OF MAKING AND USING THE SAME
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Paragraph 0080-0081, (2021/09/26)
Described herein is a method to synthesize a perfluorinated allyl ether compound of formula (I) or a perfluorinated allyl amine compound of formula (II) Where Rf1 and Rf2 are (i) independently selected from a perfluorinated alkyl group comprising 1-7 carbon atoms, a perfluorinated aryl group comprising a 5- or 6-membered ring, or combinations thereof, and optionally comprising one or more catenated heteroatoms selected from N or O; or (ii) bonded together to form a perfluorinated ring structure having 4-8 ring carbon atoms, optionally comprising at least one catenated O or N atom; and Rf3 is a perfluorinated alkyl group comprising 1-3 carbon atoms. The resulting perfluorinated allyl ether compounds disclosed herein may be used in polymer synthesis.
