Electric discharge synthesis of phosphorus compounds

Albrand, J. P.; Anderson, Steven P.; Goldwhite, Harold; Huff, L.C.

doi:10.1021/ic50145a025

Cited by 18 publications

(7 citation statements)

References 3 publications

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“…Electric discharge experiments involving phosphine were also performed by Albrand et al (1975), who, like Bossard et al (1986), report a number of discharge products including diphosphine, hydrogen and an unidentified solid. Discharge experiments involving methylphosphine yielded phosphine, diphosphine, dimethylphosphine [(CH 3 ) 2 PH] and two other products: methyldiphosphine (CH 3 PHPH 2 ) and 1,2-dimethyldiphosphine (CH 3 PHPH CH 3 ).…”

Section: Phosphorus Chemistry Spark Experimentsmentioning

confidence: 99%

Storm clouds on Saturn: Lightning-induced chemistry and associated materials consistent with Cassini/VIMS spectra

Baines

Delitsky

Momary

et al. 2009

Planetary and Space Science

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Section: Phosphorus Chemistry Spark Experimentsmentioning

confidence: 99%

Storm clouds on Saturn: Lightning-induced chemistry and associated materials consistent with Cassini/VIMS spectra

Baines

Delitsky

Momary

et al. 2009

Planetary and Space Science

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“…By complexation with borane, the phosphorus atom is protected against electrophiles such as alkyl halides or dioxygen, and activation of the hydrogen͑s͒ on the phosphorus atom is observed. 4 On the other hand, the kinetically unstabilized primary ␣ , ␤-unsaturated phosphines were synthesized for the first time in the 1980s, 8,9 and several specific physicochemical properties have been evidenced. Infrared, NMR, and microwave spectra have been reported.…”

Section: Introductionmentioning

confidence: 99%

Vinylphosphine-borane: Synthesis, gas phase infrared spectroscopy, and quantum chemical vibrational calculations

Khater

Guillemin

Bénidar

et al. 2008

The Journal of Chemical Physics

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Both experimental and theoretical investigations are reported on the infrared spectrum of vinylphosphine-borane (CH(2)=CHPH(2) x BH(3)), a donor-acceptor complex. The gas phase infrared spectra (3500-600 cm(-1)) have been recorded at 0.5 cm(-1) resolution. This first primary alpha,beta-unsaturated phosphine-borane synthesized up to now is kinetically very unstable in the gas phase and decomposes rapidly into two fragments: the free vinylphosphine CH(2)=CHPH(2) and the monoborane BH(3) which dimerizes to form the more stable diborane B(2)H(6). Spectra of free CH(2)=CHPH(2) and B(2)H(6) compounds were also recorded to assign some vibration modes of the complex in very dense spectral regions. The analysis was completed by carrying out quantum mechanical calculations by density functional theory method at the B3LYP/6-31+G(**) level. Anharmonic frequencies and infrared intensities of the two predicted gauche and syn conformers of the vinylphosphine-borane complex were calculated in the 3500-100 cm(-1) region with the use of a variational approach, implemented in the P_ANHAR_V1.2 code. Because of the relatively weak interaction between the vinylphosphine and the monoborane, the vibrations of the complex can easily be subdivided into modes localized in the CH(2)=CHPH(2) and BH(3) moieties and into "intermolecular" modes. Localized modes are unambiguously correlated with the modes of the isolated monomers. Therefore, they are described in terms of the monomer vibrations, and the complexation shifts are defined as Delta nu = nu(complex) - nu(monomer) to make the effect of the complexation precise on each localized mode. In this objective, anharmonic frequencies and infrared intensities of the BH(3) monomer and the stable gauche and syn conformers of the free vinylphosphine were obtained at the same level of theory. In the gas phase, only the syn form of the complex was observed and assigned. All theoretically predicted frequencies and complexation shifts in magnitude and direction are in good agreement with experiment. By infrared spectroscopy assisted by quantum chemical calculations, the consequences of the complexation of an alpha,beta-unsaturated phosphine by borane on the physicochemical properties of the formed 12-atom complex have been efficiently evaluated.

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“…The successful preparation of diphosphorus tetrachloride by electric discharge in mixtures of phosphorus trichloride and hydrogen21 has stimulated the recent synthesis of 1,2-dimethyldiphosphine by low-pressure silent electric discharge. 22 For this molecule, which can exist in both the meso and dj diastereomers, there are a number of possible conformers, which previous studies have shown may be most readily investigated by a study of its vibrational spectra.4,6 These conformers exist in both the trans and gauche forms, and illustrations representative of each form for similarly substituted diphosphines may be found in the literature. 13,18,19 In this paper, we present results obtained from the infrared and Raman spectra on the structure of 1,2-dimethyldiphosphine.…”

Section: Introductionmentioning

confidence: 99%

“…Experimental Section 1,2-Dimethyldiphosphine was prepared by passing methylphosphine through a silent electric discharge using a Siemans-type discharge tube. 22 The methylphosphine was prepared by the reduction of dimethyl methylphosphonate with LiAlH4 in monoglyme. 23 All sample preparations and manipulations were carried out using standard high-vacuum techniques due to the toxicity of these compounds in general, their ease of oxidation, and the thermal instability of 1,2dimethyldiphosphine.…”

Section: Introductionmentioning

confidence: 99%