- Synthesis of perfluorodiphenylphosphinic acid and its potassium and oxonium salts; crystal structure of oxonium perfluorodiphenylphosphinate
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The syntheses of perfluorodiphenylphosphinic acid, oxonium perfluorodiphenylphosphinate (perfluorodiphenylphosphinic acid monohydrate), and the potassium salt are described. Crystals of (C6F5)2PO-2H3O+ [(C6F5)2PO(OH)·H2O] are monoclinic, a = 33.541(2) A, b = 6.512(3) A, c = 30.238(2) A, Z = 16, space group C2/c. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = Rw = 0.037 for 3792 reflections with 1≥3σ(1), respectively. The crystal structure contains H3O+ cations and (C6F5)2PO-2 anions (two of each per asymmetric unit), linked by two strong, symmetrical hydrogen bonds (O...O≈2.4 A) and four more-normal hydrogen bonds (O...O≈2.6 A). P-C bonds are longer and P-O bonds shorter than in the perhydro analog.
- Oliver, Katherine W.,Rettig, Steven J.,Thompson, Robert C.,Trotter, James,Xia, Shihua
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Read Online
- Axially Chiral, Electrophilic Fluorophosphonium Cations: Synthesis, Lewis Acidity, and Reactivity in the Hydrosilylation of Ketones
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Axially chiral [(C6F5)3PF][B(C6F5)4] analogues based on dihydrophosphepines with a binaphthyl backbone were prepared and structurally characterized by X-ray diffraction analysis. Computational calculations of FIA and GEI values attest that these new fluorophosphonium cations have a higher Lewis acidity compared to the ubiquitous B(C6F5)3. Furthermore, application of these highly electrophilic compounds in the catalytic hydrosilylation of ketones and an investigation of the mechanism lead to a refined picture of the role of highly electrophilic fluorophosphonium cations.
- Süsse, Lars,Lafortune, James H. W.,Stephan, Douglas W.,Oestreich, Martin
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supporting information
p. 712 - 721
(2019/02/17)
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- Silylium ion/phosphane lewis pairs
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The reactivity of a series of silylium ion/phosphane Lewis pairs was studied. Triarylsilylium borates 4[B(C6F5)4] form frustrated Lewis pairs (FLPs) of moderate stability with sterically hindered phosphanes 2. Some of these FLPs are able to cleave dihydrogen under ambient conditions. The combination of bulky trialkylphosphanes with triarylsilylium ions can be used to sequester CO2 in the form of silylacylphosphonium ions 12. The ability to activate molecular hydrogen by reaction of silylium ion/phosphane Lewis pairs is dominated by thermodynamic and steric factors. For a given silylium ion increasing proton affinity and increasing steric hindrance of the phosphane proved to be beneficial. Nevertheless, excessive steric hindrance leads to a breakdown of the dihydrogen-splitting activity of a silylium/phosphane Lewis pair.
- Reissmann, Matti,Schaefer, Andre,Jung, Sebastian,Mueller, Thomas
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p. 6736 - 6744
(2014/01/06)
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- A new synthesis of triarylsilylium ions and their application in dihydrogen activation
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Well-shuffled: An unexpected substituent distribution reaction via alkyldiarylsilylium ions leads to a distribution of substituents. Starting from alkyldiaryl silanes, this reaction provides a facile synthetic approach to sterically highly hindered triarylsilylium ions. These silylium ions can be applied in dihydrogen activation reactions. Copyright
- Schaefer, Andre,Reissmann, Matti,Schaefer, Annemarie,Saak, Wolfgang,Haase, Detlev,Mueller, Thomas
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supporting information; experimental part
p. 12636 - 12638
(2012/02/15)
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- 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)
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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.
- Frohn, Hermann-Josef,Wenda, André,Fl?rke, Ulrich
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experimental part
p. 5762 - 5767
(2010/10/01)
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- The Acceptor Properties of some Pentafluorophenylphosphorous(V) Species
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The acceptor properties of P(C6F5)nCl5-n (1 + (1 + towards Lewis bases, such as the chloride ion and uni- and bi-dentate pyridines, have been investigated.Several new complexes have been isolated, and characterised by elemental analysis and (in some cases) 31P n.m.r. and/or i.r. spectroscopy.
- Ali, Rusmidah,Dillon, Keith B.
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p. 1375 - 1381
(2007/10/02)
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- Organothallium compounds. VI. Reactions of bromobis(pentafluorophenyl)thallium(III) with main group elements
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Bromobis(pentafluorophenyl)thallium(IlI) reacts with many main group elements on heating in the absence of a solvent to give pentafluorophenyl derivatsves of these elements. The compounds C6F5M (M = Cl, Br, or I), (C6F5)2M (M = Zn, Cd, Hg, S, Se or Te), (C6F5)3M (M = In, P, As, or Sb), and (C6F5)M (M = Ge or Sn) have been prepared by this method. Substantial decomposition of (C6F5)2TlBr occurs on reaction with aluminium, gallium, lead and bismuth, but pcntafluorophenyl derivatives of these elements are not obtained.
- Deacon,Parrott
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p. 287 - 295
(2008/10/08)
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