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  • 1
    Publication Date: 1983-01-01
    Print ISSN: 0044-2313
    Electronic ISSN: 1521-3749
    Topics: Chemistry and Pharmacology
    Published by Wiley
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  • 2
    Publication Date: 1981-02-01
    Print ISSN: 0044-2313
    Electronic ISSN: 1521-3749
    Topics: Chemistry and Pharmacology
    Published by Wiley
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  • 3
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Phosphorus. 117. Synthesis and Properties of the Hexaorganyl-octaphosphanes(6) P8R6, R = Me, Et, PriThe Hexaorganyl-octaphosphanes(6) P8Me6 (1), P8Et6 (2), and P8Pr6i (3) have been obtained by reacting mixtures of the corresponding organyldichlorophosphanes and phosphorus(III) chloride with magnesium. In the case of 1 and 2 the organyl-cyclophosphanes (PR)n can also be used in the reaction with phosphorus(III) chloride and magnesium. Besides, mainly P7R5 as well as other polycyclic organylphosphanes are formed. 2 and 3 have been isolated as pure substances, whereas 1 was concentrated to ≃50 mol-% in the product mixture. According to their 31P-NMR spectra the three compounds possess a pentalane-analogous P8-skeleton with the substituents within each five-membered ring in trans position and the substituents of different five-membered rings next to the zero bridge in cis position; the organyl groups in the 3, 7 position are trans oriented with respect to the free electron pairs of the bridgehead atoms. Therefore, the structures of 1-3 differ from the known tert-butyl compound P8Bu6t, whereas the corresponding phosphorus hydride P8H6 has the same pentalane-analogous P8-skeleton, thus being a bicyclo[3.3.0]octaphosphane.
    Notes: Die Hexaorganyl-octaphosphane(6) P8Me6 (1), P8Et6 (2) und P8Pr6i (3) werden durch Reaktion von Gemischen aus den entsprechenden Organyldichlorphosphanen und Phosphor(III)-chlorid mit Magnesium erhalten. Im Fall von 1 und 2 können auch die Organylcyclophosphane (PR)n mit Phosphor(III)-chlorid und Magnesium umgesetzt werden. Daneben entstehen vor allem P7R5 sowie weitere mehrfachcyclische Organylphosphane. 2 und 3 wurden als Reinsubstanzen isoliert, 1 auf ≃50 Mol-% im Produktgemisch angereichert. Alle drei Verbindungen besitzen aufgrund ihrer Kernresonanzspektren ein Pentalan-analoges P8-Gerüst mit trans-ständigen Substituenten innerhalb jedes Fünfringes und cis-Stellung der zur Nullbrücke benachbarten Substituenten unterschiedlicher Fünfringe; die Organylgruppen in 3,7-Position sind dabei trans-ständig zu den freien Elektronenpaaren der Brückenkopfatome angeordnet. 1-3 unterscheiden sich demnach strukturell von der schon bekannten tert-Butylverbindung P8Bu6t, während das entsprechende Phosphorhydrid P8H6 das gleiche Pentalan-analoge P8-Gerüst besitzt, also ein Bicyclo[3.3.0]octaphosphan ist.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the chemistry of phosphorus. 100. Pentamethyl-heptaphosphane(5), P7(CH3)5, and pentamethyl-nonaphosphane(5), P9(CH3)5Two new methylphosphanes with condensed ring systems, P7(CH3)5 (1) and P9(CH3)5 (2), have been obtained by reacting mixtures of phosphorus(III) chloride with methyldichlorophosphane or pentamethylcyclopentaphosphane in presence of magnesium. Besides, the formation of P7(CH3)3, P8(CH3)6 and P11(CH3)5 has been detected. 1 and 2 can be isolated in a pure state and have been characterized by elemental analysis, mass, IR, and NMR spectra as compounds with a norbornane-analogous P7-skeleton and a noradamantane-analogous P9-skeleton, respectively. Thereby, at the same time the structures of the hydrides P7H5 and P9H5 have unambiguously been clarified as bicyclo[2.2.1]heptaphosphane and tricyclo[3.3.1.03,7]nonaphosphane, respectively. 1 and 2 are formed as mixtures of various configurational isomers which differ in the arrangement of the methyl groups.
    Notes: Zwei neue mehrfachcyclische Methylphosphane, P7(CH3)5 (1) und P9(CH3)5 (2), werden durch Reaktion von Gemischen aus Methyldichlorphosphan bzw. Pentamethyl-cyclopentaphosphan und Phosphor(III)-chlorid mit Magnesium erhalten. Daneben kann die Bildung von P7(CH3)3, P8(CH3)6 und P11(CH3)5 nachgewiesen werden. 1 und 2 sind in Reinsubstanz isolierbar und wurden durch Elementaranalyse, Massenspektrum, IR-Spektrum und Kernresonanzspektren als Verbindungen mit Norbornan-analogem P7-Gerüst bzw. Noradamantan-analogem P9-Gerüst charakterisiert. Damit sind zugleich die Strukturen der Hydride P7H5 und P9H5 als Bicyclo[2.2.1]heptaphosphan bzw. Tricyclo[3.3.1.03,7]nonaphosphan eindeutig geklärt. 1 und 2 entstehen als Gemische von verschiedenen Konfigurationsisomeren, die sich in der räumlichen Anordnung der Methylgruppen unterscheiden.
    Additional Material: 4 Ill.
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