22474-72-2Relevant academic research and scientific papers
Electrophilic Phosphonium Cations as Lewis Acid Catalysts in Diels-Alder Reactions and Nazarov Cyclizations
Vogler, Maria,Süsse, Lars,Lafortune, James H. W.,Stephan, Douglas W.,Oestreich, Martin
, p. 3303 - 3313 (2018)
The highly electrophilic fluorophosphonium cation [(C6F5)3PF]+[B(C6F5)4]- is shown to catalyze Diels-Alder reactions of challenging dienophile/enophile combinations an
Probing steric influences on electrophilic phosphonium cations: A comparison of [(3,5-(CF3)2C6H3)3PF]+ and [(C6F5)3PF]+
Lafortune, James H. W.,Szkop, Kevin M.,Farinha, Farah E.,Johnstone, Timothy C.,Postle, Shawn,Stephan, Douglas W.
supporting information, p. 11411 - 11419 (2018/08/28)
The electrophilic phosphonium cation (EPC) salt [(3,5-(CF3)2C6H3)3PF][B(C6F5)4] (2) is prepared via oxidation of the precursor phosphine with XeF2 and subse
Difluorotriorganylphosphoranes for the Synthesis of Fluorophosphonium and Bismuthonium Salts
Solyntjes, Sven,Neumann, Beate,Stammler, Hans-Georg,Ignat'ev, Nikolai,Hoge, Berthold
, p. 3999 - 4010 (2016/09/13)
Fluoride ion affinities (FIA), provided by DFT calculations, are exceedingly useful for the design of new Lewis acids with defined reactivities. Herein, we report the synthesis, characterization and reactivity of new difluoro(perfluoroorganyl)phosphoranes, which readily abstract fluoride ions from difluoro(triorganyl)phosphoranes. Highly reactive fluorobismuthonium cations and the [Ph3Bi(NCCH3)2]2+cation are accessible through the treatment of difluoro(triorganyl)bismuth(V) compounds with the Lewis acidic phosphoranes discussed here.
Electrophilic phenoxy-substituted phosphonium cations
LaFortune, James H. W.,Johnstone, Timothy C.,Pérez, Manuel,Winkelhaus, Daniel,Podgorny, Vitali,Stephan, Douglas W.
supporting information, p. 18156 - 18162 (2016/11/25)
A family of electrophilic phenoxy-substituted phosphonium salts [(RO)P(C6F5)3][B(C6F5)4] (R = C6H5, 4-FC6H4, 2,4-F2C6H3, C6F5) have been synthesized and their air stability was evaluated. Computations of the fluoride ion affinity and global electrophilicity index have been used to compare the electrophilicity of these phosphonium salts. The Lewis acidity of these phosphonium salts was probed computationally and experimentally in a Friedel-Crafts-type dimerization, hydrodefluorination, hydrosilylation, hydrodeoxygenation, and dehydrocoupling reactions.
Xenon(IV)-carbon bond of [C6F5XeF2]+; Structural characterization and bonding of [C6F5XeF2][BF4], [C6F5XeF2][BF4]·2HF, and [C6F5XeF2][BF4]· n NCCH 3 (n = 1, 2); And the fluorinating properties of [C6F5XeF2][BF4]
Koppe, Karsten,Haner, Jamie,Mercier, Hlne P. A.,Frohn, Hermann-J.,Schrobilgen, Gary J.
, p. 11640 - 11661 (2015/01/16)
The [C6F5XeF2]+ cation is the only example of a XeIV-C bond, which had only been previously characterized as its [BF4]- salt in solution by multi-NMR spectroscopy. The [BF4]- salt and its new CH3CN and HF solvates, [C6F5XeF2][BF4]·1.5CH3CN and [C6F5XeF2][BF4]·2HF, have now been synthesized and fully characterized in the solid state by lowerature, single-crystal X-ray diffraction and Raman spectroscopy. Crystalline [C6F5XeF2][BF4] and [C6F5XeF2][BF4]·1.5CH3CN were obtained from CH3CN/CH2Cl2 solvent mixtures, and [C6F5XeF2][BF4]·2HF was obtained from anhydrous HF (aHF), where [C6F5XeF2][BF4]·1.5CH3CN is comprised of an equimolar mixture of [C6F5XeF2][BF4]·CH3CN and [C6F5XeF2][BF4]·2CH3CN. The crystal structures show that the [C6F5XeF2]+ cation has two short contacts with the F atoms of [BF4]- or with the F or N atoms of the solvent molecules, HF and CH3CN. The lowerature solid-state Raman spectra of [C6F5XeF2][BF4] and C6F5IF2 were assigned with the aid of quantum-chemical calculations. The bonding in [C6F5XeF2]+, C6F5IF2, [C6F5XeF2][BF4], [C6F5XeF2][BF4]·CH3CN, [C6F5XeF2][BF4]·2CH3CN, and [C6F5XeF2][BF4]·2HF was assessed with the aid of natural bond orbital analyses and molecular orbital calculations. The 129Xe, 19F, and 11B NMR spectra of [C6F5XeF2][BF4] in aHF are reported and compared with the 19F NMR spectrum of C6F5IF2, and all previously unreported J(129Xe-19F) and J(19F-19F) couplings were determined. The long-term solution stabilities of [C6F5XeF2][BF4] were investigated by 19F NMR spectroscopy and the oxidative fluorinating properties of [C6F5XeF2][BF4] were demonstrated by studies of its reactivity with K[C6F5BF3], Pn(C6F5)3 (Pn = P, As, or Bi), and C6F5X (X = Br or I).
Lewis acidity of organofluorophosphonium salts: Hydrodefluorination by a saturated acceptor
Caputo, Christopher B.,Hounjet, Lindsay J.,Dobrovetsky, Roman,Stephan, Douglas W.
, p. 1374 - 1377 (2013/10/08)
Prototypical Lewis acids, such as boranes, derive their reactivity from electronic unsaturation. Here, we report the Lewis acidity and catalytic application of electronically saturated phosphorus-centered electrophilic acceptors. Organofluorophosphonium salts of the formula [(C6F 5)3-xPhxPF][B(C6F5) 4] (x = 0 or 1; Ph, phenyl) are shown to form adducts with neutral Lewis bases and to react rapidly with fluoroalkanes to produce difluorophosphoranes. In the presence of hydrosilane, the cation [(C 6F5)3PF]+ is shown to catalyze the hydrodefluorination of fluoroalkanes, affording alkanes and fluorosilane. The mechanism demonstrates the impressive fluoride ion affinity of this highly electron-deficient phosphonium center.
A first methodical approach to salts with unsymmetrical fluorophenyl(pentafluorophenyl)difluoroiodonium(V) cations [Rf(R F)IF2]+ (Rf=x-FC6H 4, x=2, 3, 4; RF=C6F5)
Frohn, Hermann-Josef,Wenda, André,Fl?rke, Ulrich
experimental part, p. 5762 - 5767 (2010/10/01)
A promising approach to the unknown type of [Ar′(Ar)IF2]X salts is offered. x-FC6H4IF4 (x=2, 3, 4) reacts with C6F5BF2 in CH2Cl2 and forms [x-FC6H4(C6F5)IF 2][BF4] salts in good yields. For [4-FC6H 4(C6F5)IF2][BF4] the fluoro-oxidizer property is shown in reactions with weakly reducing agents like E(C6F5)3 (E=P, As, Sb, Bi) and ArI (Ar=4-FC6H4, C6F5). The fluorine/aryl substitution method is also applied to the synthesis of [(4-FC6H4)2IF2][BF4], an example with two identical aryl groups in the difluoroiodonium(V) moiety.
BEITRAEGE ZUR CHEMIE DES IODOPENTAFLUORIDS. TEIL IV. IF5 EIN SELEKTIVES OXIDATIVES FLUORIERUNGSMITTEL FUER ORGANOPHOSPHOR(III)-VERBINDUNGEN
Frohn, H. J.,Maurer, H.
, p. 73 - 82 (2007/10/02)
Aryl-and alkylphosphines R3P, R2PF, R2PCl, and RPCl2 are oxidized by IF5 to the corresponding fluorophosphoranes in a fast one step-reaction at or below 0 deg C.The only coproduct is elemental iodine.IF3 or IF as reduction products of IF5 are not observed.Fission of P-C - bonds by from I2 and IF5 is negligible under reaction conditions.In alkylfluorophosphoranes fluoride donor-acceptor-interactions between fluorophosphoranes and IF5 are observed.
