Cleavage of P P Bonds in Phosphorus. An Efficient Method for the Preparation of Primary Alkylphosphines

Brandsma, L.; Doom, Johanes A. van; Lang, Robert-Jan de; Гусарова, Н. К.; Трофимов, Б. А.

doi:10.1070/mc1995v005n01abeh000438

Cited by 22 publications

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“…The use of P, Li, and ButOH in a molar ratio of 1 : 3 : 2 leads to the predominant formation of monophosphide anions, whose reactions with organyl halides have resulted in the synthesis of primary phosphines 1 ill 72--87% yields (Scheme 2). 7,13,14 Oxirane can also be used as the electrophile in this reaction; this compound is phosphorylated by the red phosphorus--alkali metaI--ButOH system in liquid NH~ to give 2-hydroxyethylphosphine in 27% yield (toot optimized) (Scheme 3 …”

Section: Synthesis Of Primary Phosphinesmentioning

confidence: 99%

Synthesis of organic phosphines and phosphine oxides from elemental phosphorus and phosphine in the presence of strong bases

et al. 1998

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Section: Synthesis Of Primary Phosphinesmentioning

confidence: 99%

Synthesis of organic phosphines and phosphine oxides from elemental phosphorus and phosphine in the presence of strong bases

et al. 1998

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Ion Dynamics in Confined Spaces: Sodium Ion Mobility in Icosahedral Container Molecules

et al. 2010

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Cation fluctuations within a molecular anionic ligand framework in crystals have rarely been observed. Veith et al. have studied local Li + ion fluctuations in crystalline lithium siloxyamides that contain either an anionic (N-Si-O-Si-N) 2À = (X 2À ) or (O-Si-N-Si-O) À = (Z À ) skeleton. [1] In the crystalline [Li 2 (Z) 2 ] and [Li 4 (X) 2 ] species, the metal movements proceed in a concerted fashion, that is, the cations jump simultaneously from filled to empty positions as electrostatically coupled (Li 2 ) 2+ and (Li 4 ) 4+ clusters, and the movements are linked to phase transitions, rotations, and oscillations of atoms and atom groups. A partial dynamic disorder of Li + ions has also been reported in the "onion"-type spherical cluster [Li 24 OI 2 (AsR) 10 ] (R = Me 2 (iPrMe 2 C)Si). [2] To date, ion fluctuations in crystallized "molecular boxes" have only been observed for Li + ions.We report herein on two compounds that are composed of a small central PH 2 À anion surrounded by a spherical outer shell consisting of twelve tert-butoxy anions. In this confined polyanionic space, that is, between the PH 2 À anion and the outer shell, 12 or 13 highly mobile sodium cations are embedded. One sodium ion can be reversibly added or removed to interconvert these aggregates.Brandsma et al. reported the synthesis of sodium dihydrogenphosphide, NaPH 2 , which uses the reduction of elemental phosphorus with sodium metal and subsequent addition of tert-butyl alcohol. This form of NaPH 2 is a versatile reagent for the preparation of organophosphorus compounds; [3] however, the nature of this "Brandsma reagent" was not known.We treated a solution of sodium in a 1:1 (by volume) mixture of ammonia and dimethoxyethane (dme) with red or white phosphorus. A yellow-brown suspension is obtained after approximately 1.5 h. After evaporation of the ammonia, the crude mixture, containing [NaPH 2 (solv) x ] and [NaNH 2 -(solv) x ] (solv = NH 3 or dme) suspended in dme, was treated with tert-butyl alcohol at À78 8C (Scheme 1 a). A clear solution is obtained at room temperature, which shows one triplet in the proton-coupled 31 P NMR spectrum at d = À307.7 ppm (J = 145.0 Hz) and a doublet at d = À2.24 ppm in the 1 H NMR spectrum (J = 145.0 Hz) for the PH 2 À ion. From this solution, colorless crystals of the composition Na 13 (dme) 3 (PH 2 )(OtBu) 12 (1) were obtained.When the crude NaPH 2 /NaNH 2 mixture is evaporated to dryness and toluene is used as solvent for the reaction with tBuOH, a new species 2 is detected by 31 P and 1 H NMR spectroscopy in the clear solution. The PH 2 À ion is identified through a triplet at d = À292.3 ppm (J = 142 Hz) in the proton-coupled 31 P NMR spectrum and a doublet at d = Scheme 1. Syntheses of 1 and 2.

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Ion Dynamics in Confined Spaces: Sodium Ion Mobility in Icosahedral Container Molecules

et al. 2010

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Cation fluctuations within a molecular anionic ligand framework in crystals have rarely been observed. Veith et al. have studied local Li + ion fluctuations in crystalline lithium siloxyamides that contain either an anionic (N-Si-O-Si- ions has also been reported in the "onion"-type spherical cluster [Li 24 OI 2 (AsR) 10 ] (R = Me 2 (iPrMe 2 C)Si).[2] To date, ion fluctuations in crystallized "molecular boxes" have only been observed for Li + ions. We report herein on two compounds that are composed of a small central PH 2 À anion surrounded by a spherical outer shell consisting of twelve tert-butoxy anions. In this confined polyanionic space, that is, between the PH 2 À anion and the outer shell, 12 or 13 highly mobile sodium cations are embedded. One sodium ion can be reversibly added or removed to interconvert these aggregates.Brandsma et al. reported the synthesis of sodium dihydrogenphosphide, NaPH 2 , which uses the reduction of elemental phosphorus with sodium metal and subsequent addition of tert-butyl alcohol. This form of NaPH 2 is a versatile reagent for the preparation of organophosphorus compounds; [3] however, the nature of this "Brandsma reagent" was not known.We treated a solution of sodium in a 1:1 (by volume) mixture of ammonia and dimethoxyethane (dme) with red or white phosphorus. A yellow-brown suspension is obtained after approximately 1.5 h. After evaporation of the ammonia, the crude mixture, containing [NaPH 2 (solv) x ] and [NaNH 2 -(solv) x ] (solv = NH 3 or dme) suspended in dme, was treated with tert-butyl alcohol at À78 8C (Scheme 1 a). A clear solution is obtained at room temperature, which shows one triplet in the proton-coupled 31 P NMR spectrum at d = À307.7 ppm (J = 145.0 Hz) and a doublet at d = À2.24 ppm in the 1 H NMR spectrum (J = 145.0 Hz) for the PH 2 À ion. From this solution, colorless crystals of the composition Na 13 (dme) 3 (PH 2 )(OtBu) 12 (1) were obtained.When the crude NaPH 2 /NaNH 2 mixture is evaporated to dryness and toluene is used as solvent for the reaction with tBuOH, a new species 2 is detected by 31 P and 1 H NMR spectroscopy in the clear solution. The PH 2 À ion is identified through a triplet at d = À292.3 ppm (J = 142 Hz) in the proton-coupled 31 P NMR spectrum and a doublet at d = Scheme 1. Syntheses of 1 and 2.

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Cleavage of P P Bonds in Phosphorus. An Efficient Method for the Preparation of Primary Alkylphosphines

Cited by 22 publications

References 9 publications

Synthesis of organic phosphines and phosphine oxides from elemental phosphorus and phosphine in the presence of strong bases

Synthesis of organic phosphines and phosphine oxides from elemental phosphorus and phosphine in the presence of strong bases

Ion Dynamics in Confined Spaces: Sodium Ion Mobility in Icosahedral Container Molecules

Ion Dynamics in Confined Spaces: Sodium Ion Mobility in Icosahedral Container Molecules

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