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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 2404-2405 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 113 (1980), S. 1264-1271 
    ISSN: 0009-2940
    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, 88. 1,2,3-Triphenyl-1,3-bis(trimethylsilyl)triphosphaneThe reaction of 1,3-dipotassium 1,2,3-triphenyltriphosphide, K2 (PPh)3, with chlorotrimethyl-silane yields the hitherto unknown title compound Me3Si(Ph)P—P(Ph)—P(Ph)SiMe3 (1), which is remarkably stable against disproportionation reactions. In solution it forms the three diastereomers 1a (erythro/erythro), 1b (erythro/threo), and 1c (threo/threo) in a ratio of about 8:3:1, between which a dynamic equilibrium exists due to pyramidal inversion at the P-atoms. The correlation between the 31P-NMR-spectroscopically observed spin systems and the diastereomers 1a-c results from the significant dependence of the 1JPP-coupling constants on dihedral angles. The preferred trans arrangement of the bulky SiMe3- and P(Ph)SiMe3 groups at adjacent P-atoms leads to a trans-conformation of the lone electron pairs in the erythro- and to a gauche-conformation in the threo-configuration.
    Notes: Die Reaktion von 1,3-Dikalium-1,2,3-triphenyltriphosphid, K2(PPh)3, mit Chlortrimethylsilan ergibt in guter Ausbeute die bislang unbekannte Titelverbindung Me3Si(Ph)P—P(Ph)—P(Ph)SiMe3 (1), die gegenüber Disproportionierungsreaktionen bemerkenswert beständig ist. Sie bildet in Lösung die drei Diastereomeren 1a (erythro/erythro), 1b (erythro/threo) und 1c (threo/threo) im Verhältnis von etwa 8:3:1, die infolge pyramidaler Inversion der P-Atome in einem dynamischen Gleichgewicht miteinander stehen. Die Korrelation zwischen den 31P-NMR-spektroskopisch beobachteten Spinsystemen und den Diastereomeren 1a-c ergibt sich aufgrund der signifikanten Torsionswinkelabhängigkeit der 1JPP-Kopplungskonstanten. Die bevorzugte trans-Anordnung der großvolumigen SiMe3- und P(Ph)SiMe3-Reste an benachbarten P-Atomen führt bei erythro-Konfiguration zu einer trans- und bei threo-Konfiguration zu einer gauche-Konformation der freien Elektronenpaare.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 1217-1220 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Contributions to the Chemistry of Phosphorus, 78: 1,2,3-TriphenyltriphosphaneAmong the disproportionation products of 1,2-diphenyldiphosphane (1), 1,2,3-triphenyltriphosphane (2) could be enriched up to the maximum concentration of ≍50% with respect to the total phosphorus. 2 was identified by the 31P{1H} NMR spectrum that exhibits, in the region of openchain triphosphanes, two A2B and one ABC spin system for the three diastereomers, of which the NMR parameters are reported. Contrary to results given in the literature, 2 is not stable at room temperature, but disproportionates to give lower and higher homologues of the series H(PPh)nH as well as cyclic phenylphosphanes, especially (PPh)5.
    Additional Material: 1 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 1210-1216 
    ISSN: 0009-2940
    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, 73: 1,2-Diphenyldiphosphane1,2-Diphenyldiphosphane (1) is formed, contrary to results given in the literature, by the reaction of KHPPh with 1,2-dibromoethane. Pure 1 is obtained by hydrolysis or alcoholysis of Me3Si(Ph)P-P(Ph)SiMe3 in the dark. It is stable at - 30°C. 1 disproportionates at room temperature to give PhPH2, higher homologues of the series H2[PPh]n, especially H2[PPh]3, and cyclic phenylphosphanes [PPh]n, mainly [PPh]5. These rearrangements are accelerated by light, phosphides, and strong acids and bases. With K(Ph)P—P(Ph)K, Me3Si(Ph)P—P(Ph)SiMe3, and P2Ph4 1 reacts to give the asymmetric diphosphanes K(Ph)P—P(Ph)H, Me3Si(Ph)P—P(Ph)H, and Ph2P—P(Ph)H, respectively. The NMR, IR, and Raman spectra are discussed.
    Notes: 1,2-Diphenyldiphosphan (1) wird - entgegen Literaturangaben - bei der Reaktion von KHPPh mit 1,2-Dibromethan gebildet. Reines 1 ist durch Hydrolyse oder Alkoholyse von Me3Si(Ph)P - P(Ph)SiMe3 unter Lichtausschluß erhältlich und bei - 30°C beständig. Es disproportioniert bei Raumtemperatur in PhPH2, höhere Homologe der Reihe H2[PPh]n  -  insbesondere H2[PPh]3 - und cyclische Phenylphosphane [PPh]n  -  vor allem [PPh]5. Diese Umlagerungen werden durch Licht, Phosphide sowie starke Säuren und Basen beschleunigt. Mit K(Ph)P—P(Ph)K, Me3Si(Ph)P—P(Ph)SiMe3 oder P2Ph4 reagiert 1 zu den unsymmetrischen Diphosphanen K(Ph)P—P(Ph)H, Me3Si(Ph)P—P(Ph)H bzw. Ph2P—P(Ph)H. Die NMR-, IR- und Raman-Spektren von 1 werden diskutiert.
    Additional Material: 1 Tab.
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