- Vinylphosphine: Synthesis by Flash Vacuum Pyrolysis, Stability, and Spectroscopic Properties
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Vinylphosphine (1) has been synthesized from diethyl vinylphosphonate in three steps including a retro cycloaddition reaction using flash vacuum pyrolysis (overall yield ca. 30percent) and characterized by mass, i.r., and n.m.r. spectroscopy; it exhibits
- Lasne, Marie-Claire,Ripoll, Jean-Louis,Thuillier, Andre
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- η-Cyclopentadienyltungsten Compounds with Vinyl- and Allyl-phosphine Ligands
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The properties as ligands of the primary phosphines PH2(CH=CH2) 1 PH2(CH2CH=CH2) 2 have been studied.The new compounds (R 5= H4-i-Pr, R'= CH=CH2 7 or CH2CH=CH2 8; R5 = Me4Et, R' = CH=CH2 9 or CH2CH=CH2 10), (X = Cl, R = CH=CH2 12 or CH2CH=CH2 13; X = Br, R = CH=CH2 15), 17 and 18 have been prepared.The crystal structures of compounds 10 and 17 have been determined.
- Morise, Xavier,Green, Malcolm L. H.,McGowan, Patrick C.,Simpson, Stephen J.
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- Rotational Spectrum, Molecular Constants, Dipole Moment, and Internal Rotation in Vinylphosphine
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The rotational spectra of both CH2=CHPH2 and CH2=CHPD2 have been measured from 8 to 320 GHz.Rotational constants, centrifugal distortion constants, and dipole moment components heve been determined.Only the gauche form (dihedral angle of 118.6 deg between the lone pair of phosphorus and the C=C bond) was found.With assumed bond lengths and bond angles for the vinyl part, the remaining structural parameters have been derived by fitting them to the six rotational constants.Structural results are compared with those of other phosphine derivatives.Internal rotation between two equivalent gauche configurations of CH2=CHPH2 causes splittings of μc transitions, which have been analyzed using the phenomenological group-theoretical Hamiltonian.
- Drean, P.,Guennec, M. Le,Lopez, J. C.,Alonso, J. L.,Denis, J. M.,et al.
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- NOVEL VINYL PHOSPHINES AND PHOTO-INITIATORS OBTAINABLE THEREFROM
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The present invention relates to a highly efficient process to prepare alkyl and vinyl phosphines which are useful as starting materials for novel bisacylphosphine oxides, bisacylphosphinic acids, salts, and derivatives thereof each bearing a vinyl functionality bound to the phosphorous atom as well as a versatile process for the preparation of the latter.
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Paragraph 38
(2019/10/04)
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- Synthesis, photoelectron spectroscopy and quantum chemical study of kinetically unstabilized phosphines complexed by borane
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Ethynyl- and allenylphosphine-boranes have been prepared by addition at low temperature of borane on the free phosphine. Purification was performed by selective trapping in vacuo and the complexes were characterized by NMR and infrared spectroscopy and ma
- Nemeth, Balazs,Khater, Brahim,Veszpremi, Tamas,Guillemin, Jean-Claude
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p. 3526 - 3535
(2009/09/07)
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- Gas-phase basicity and acidity trends in α,β-unsaturated amines, phosphines, and arsines
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The acidity and basicity trends in the series of α,β-unsaturated amines, phosphines, and arsines were analyzed through the use of G2 ab initio calculations and the examination of experimental data obtained by means of FT-ICR techniques. The α,β-unsaturated amines, phosphines, and arsines are less basic but significantly more acidic than the corresponding saturated analogues. However, while both vinyl- and ethynylamine protonate preferentially at the β-carbon atom, vinyl- and ethynylphosphine are phosphorus bases in the gas-phase. Arsines resemble closely the corresponding phosphines, although protonation at the Ca atom competes with protonation at the heteroatom. The enhanced acidity of unsaturated compounds can be attributed essentially to a stabilization of the anions because of a favorable interaction of the XH- group with the C-C multiple bonds. This stabilizing effect is maximum for amines and minimum for arsines. The low relative basicity of these unsaturated compounds results from a destabilization of the protonated species due to unfavorable interactions of the XH3+ group with the C-C π-system. Protonation at the β-carbon is strongly favored for amines but unfavorable for phosphines and arsines, because the carbocation formed is much less stabilized when the heteroatom of the XH2 group belongs to the second or the third-row than when it is a first-row atom.
- Mó, Otilia,Yá?ez, Manuel,Decouzon, Michèle,Gal, Jean-Fran?ois,Maria, Pierre-Charles,Guillemin, Jean-Claude
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p. 4653 - 4663
(2007/10/03)
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- Preparative synthesis of primary vinylphosphines by chemoselective reduction of the corresponding vinylphosponates
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Primary vinylphosphines which were described as highly polymerisable compounds in the literature are prepared on gram scale in one step by a chemoselective reduction of the corresponding vinylphosphonates.They exhibit a surprising stability.
- Cabioch, J. L.,Denis, J. M.
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p. 227 - 234
(2007/10/02)
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- Ethenylphosphine. Synthesis by Flash-Vacuum Thermolysis and Characterization by Photoelectron Spectroscopy
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Ethenylphosphine and prop-1-en-2-ylphosphine, obtained by flash-vacuum thermolysis of the corresponding Diels-Alder adducts, have been characterized by their photoelectron spectra.In both cases, the broad shape of the first two bands respectively at 9.65 and 10.85 eV for ethenylphosphine and at 9.50 and 10.3 eV for prop-1-en-2-ylphosphine can only be accounted for if we assume a free-rotating P-C bond.This conclusion was inferred from a complete theoretical study of the rotation process of the PH2 group around the P-C bond.Two privileged forms were found: a syn form (Φ = o, the lone pair of the phosphorus eclipsing the P-C bond) and a gauche form 3.5 kJ*mol-1 less stable (Φ = 127o), separated by low rotation barriers (8.19 and 10.74 kJ*mol-1).Evaluation of the accurate ionization potentials according to a configuration interaction formalism has been achieved for ethenylphosphine in different conformations.The results of these calculations clearly indicate that during the rotation process the energy of the first two ionic states extends over a 0.4 eV interval.
- Gonbeau, Danielle,Lacombe, Sylvie,Lasnes, Marie-Claire,Ripoll, Jean-Luis,Pfister-Guillouzo, Genevieve
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p. 2730 - 2735
(2007/10/02)
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- RETRODIENIC REACTIONS. PART 2. VINYL- AND PROPENYL-PHOSPHINES: SYNTHESIS BY FLASH VACUUM THERMOLYSIS AND CHARACTERIZATION
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The primary unsaturated phosphines, vinylphosphine (1), isopropenylphosphine (2) and (E)-prop-1-enylphosphine (3) have been synthesized by flash vacuum thermolysis of their formal Diels-Alder adducts with anthracene, cyclopentadiene, or 1,3-diphenylisoben
- Lasne, Marie-Claire,Ripoll, Jean-Louis,Thuillier, Andre
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