1153-05-5Relevant articles and documents
Versatile reagent Ph3As(OTf)2: One-pot synthesis of [P7(AsPh3)3][OTf]3 from PCl3
Donath, Maximilian,Bodensteiner, Michael,Weigand, Jan J.
, p. 17306 - 17310 (2014)
Compound Ph3As(OTf)2 as a pentacoordinated AsV Lewis acid readily forms dicationic Lewis acid/base ad-ducts upon addition of various Lewis bases. It also represents a stronger chloride-abstracting agent than Me3SiOTf and facilitates the reductive coupling of PCl3 in the presence of AsPh3 to the unprecedented cation [P7(AsPh3)3]3+ as triflate salt. This crystallographically characterized nor-tricyclane-type cation represents a P7R3-derivative with the most electron-withdrawing substituents, resulting in a pronounced effect on the structural parameters of the P7 core.
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Luckenbach
, p. 307 (1973)
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Oxidations of ER3 (E = P, As, or Sb) by hydrogen peroxide. Methylrhenium trioxide as catalyst
Abu-Omar,Espenson
, p. 272 - 280 (1995)
Catalytic and noncatalytic conversions of tertiary phosphines to their oxides by hydrogen peroxide have been investigated. The catalyst is methylrhenium trioxide, CH3ReO3. The kinetics were investigated in acetonitrile-water (1:1 by volume) at 25°C. Stepwise interactions between CH3ReO3 and H2O2 form CH3Re(η2-O2)(O)2(OI2). A, and CH3Re(η2-O2)2(O)(OH2), B. In CH3CN-H2O (1:1 v/v) the equilibrium constants are K1 = 13 ± 2 L mol-1 and K2 = 136 ± 28 L mol-1 at pH 1.0 and 25°C. The forward and reverse rate constants for the formation of A in this medium are k1 = 32.5 ± 0.3 L mol-1 s-1 and k-1 - 3.0 ± 0.2 s-1. Systematic changes in the substituents on phosphorus were made to vary the nucleophilicity of the phosphine and its cone angles; the kinetic effects are discernible, although they lie in a narrow range. Triphenylarsine and triphenylstibine were also studied, and their rates are within a factor of 2 of that for PPh3. The rhenium peroxides A and B show a small difference in reactivity. The bimolecular reactions between A and most of the phosphines have rate constants of the order 105 L mol-1 s-1. The kinetic data support a mechanism that allows nucleophilic attack of the substrate at the rhenium peroxides.
Organobismuth compounds. VI. Preparation and characterization of cationic complexes of triphenylbismuth(V) derivatives
Beaumont,Goel,Prasad
, p. 944 - 947 (1973)
Pentacoordinate cationic complexes of the types (Ph3BiL2)X2 and [(Ph3BiL)2O]X2, where L = DMSO, pyO, Ph3PO, or Ph3AsO and X = ClO4, BF4, or PF6, have been isolated and characterized by elemental analyses, infrared spectral, and conductance measurements. An unstable complex [Ph3Bi(Ph3AsO)2](NO3)2 has also been prepared and characterized by infrared spectroscopy. The Bi-O stretching frequencies for these complexes have been assigned, except for complexes containing Ph3PO. In dichloromethane, the complex [Ph3Bi(Ph3AsO)2]BF4 decomposes into Ph3BiF2 and Ph3AsOBF3 and the complexes [(Ph3BiL)2O](ClO4)2, where L = DMSO or pyO, appear to dissociate according to the equation [(Ph3BiL)2O](ClO4)2 ? [Ph3Bi(OClO3)]2O + 2L. No dissociation is indicated for other complexes. The complexes Ph3BiPh3Bi(Ph3AsO)2X2, where X = BF4 or PF6, form solvates with ketones such as acetone, diethyl ketone, and acetylacetone. Infrared and nmr data for these solvates indicate that the ketone is not coordinated to bismuth.
REACTIONS OF TRIPHENYLARSINE OXIDE WITH AQUEOUS HYDROGEN FLUORIDE: CRYSTAL STRUCTURE OF BIS(TRIPHENYLARSINE OXIDE)HYDROGEN(I) TETRAFLUOROBORATE
Glidewell, C.,Harris, G. S.,Holden, H. D.,Liles, D. C.,McKechnie, J. S.
, p. 143 - 154 (1981)
Fluorination of triphenylarsine oxide by aqueous hydrogen fluoride (1-40percent) in the absence of glass readily gives triphenylarsine difluoride.When the reaction with dilute (1percent) aqueous hydrogen fluoride is carried out in borosilicate glass apparatus, the glass participates in the reaction resulting in the formation of the crystalline 2:1 adduct 2Ph3AsO*HBF4.Crystals of this compound are monoclinic, P21/c, a = 12.926(4), b = 17.819(6), c = 14.994(4) Angstroem, β = 98.97(3) deg, Z = 4.The structure contains cations (1+) in which O....O is 2.44(2) Angstroem, and anions BF4-.
Kinetic and Computational Studies of Rhenium Catalysis for Oxygen Atom Transfer Reactions
Ibdah, Abdellatif,Bakar, Heba Bani,Alduwikat, Salwa
, p. 149 - 159 (2018/03/09)
The rhenium(v)oxo dimer {MeReO(edt)}2 (edt≤1,2-ethanedithiolate) is an effective catalyst for the oxygen atom transfer (OAT) reaction from pyridine oxide and picoline oxide to triphenylarsine (Ph3As) as oxygen acceptor. Kinetics measurements were carried
Studies on the peroxo complexes of thorium (IV) containing organic acids and amine bases
Nasrin, Jahanara,Saidul Islam
experimental part, p. 65 - 71 (2010/08/07)
New peroxo complexes of Th(IV) have been synthesized and characterized by elemental analyses and various physicochemical techniques. The complexes were found to oxidize allyl alcohol and triphenylphosphine as well as triphenylarsine to their respective oxides. The molar conductance values and six fold coordination indicate that all the complexes are 1:1 electrolytes in dimethylsulphoxide revealing their ionic characters. The complexes display v(C=0) bands at-1625 cm-1 and v(C-O) bands at-1405 cm-1, significantly lower than the values of amino acid (-1630 cm-1 and -1412 cm-1) indicating the coordination of amino acids through their carboxylate anion. The Th(IV) complexes display v(M=O) modes in the region 910-999 cm-1. The broad band observed at about 3244-3386 cm -1 for v(N-H) modes indicates the coordination of amino group through nitrogen atom of amino acid. These are predominantly O-O stretching V 1, the symmetric M-O stretch V2 and the antisymmetric M-O stretch V3. The characteristic V1(O-O) modes of the complexes appear at 800-840 cm-1. It is observed that the V 1 mode decreases with the increase of atomic number of the metal in a particular group. The magnetic moment values of dioxothorium (IV) complexes revealed them to be diamagnetic in nature, suggesting there were no changes in the oxidation states of the metal ions upon complexation. The electronic spectral data of the complexes showed bands at 260-350 nm region due to the charge transfer band only.
