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  • 1
    ISSN: 0044-2313
    Keywords: Diphosphane(4) ; Phosphinophosphinic Acid ; Bis(phosphino)phosphinic Acid ; Cumene Hydroperoxide ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Phosphorus. 237. On the Reaction of Diphosphane(4) with Peroxo Compounds: Formation of Phosphinophosphinic Acid, H2PPH(O)OH, and Bis(phosphino)phosphinic Acid, (H2P)2P(O)OHDiphosphane(4) reacts with peroxo compounds such as hydrogen peroxide, tetraline hydroperoxide, trifluoroperoxyacetic acid, and cumene hydroperoxide (which is particularly suited for preparative work) at -30°C to furnish phosphino-phosphinic acid, H2PPH(O)OH (1), as the primary product. Compound 1 disproportionates to a major extent in statu nascendi to give phosphanes (above all PH3) and monophosphorus acids of various oxidation states as well as some bis(phosphino)phosphinic acid, (H2P)2P(O)OH (2). The acids 1 and 2 can be trapped and stabilized as their triethylammonium salts. The structures of these salts have been determined by spectroscopic investigations.
    Notes: Diphosphan(4) reagiert mit Peroxoverbindungen, wie Wasserstoffperoxid, Tetralinhydroperoxid, Trifluorperessigsäure und Cumolhydroperoxid (präparativ besonders günstig), bei -30°C unter Bildung von Phosphinophosphinsäure, H2PPH(O)OH (1), als Primärprodukt. Verbindung 1 disproportioniert bereits größtenteils in statu nascendi, wobei Phosphane (vor allem PH3) und Monophosphorsäuren unterschiedlicher Oxydationsstufen sowie etwas Bis(phosphino)phosphinsäure, (H2P)2P(O)OH (2), entstehen. Die Säuren 1 und 2 können als Triethylammoniumsalze abgefangen und stabilisiert werden. Ihre Strukturen wurden durch spektroskopische Untersuchungen ermittelt.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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  • 2
    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. 74. 1,1-Diphenyldiphosphane and Monophenyldiphosphane by Reaction of Diphosphane with Tetraphenyldiphosphane resp. 1,2-DiphenyldiphosphaneDiphosphane reacts with tetraphenyldiphosphane in tetrahydrofuran or carbon disulfide under formation of 1,1-Diphenyldiphosphane, (C6H5)2P—PH2 1 even at -78°C. Simultaneously diphenylmonophosphane appears as a disproportionation-product of 1. Above +40° the reaction of diphosphane with 1,2-Diphenyldiphosphane in tetrahydrofuran leads to monophenyldiphosphane, (C6H5)HP—PH2 2. Using proper reaction conditions the disproportionation of the initial compounds as well as of 2 can be widely reduced. The mentioned reactions for the formation of 1 and 2 very probably occur via fourcenter transition states.
    Notes: Diphosphan reagiert mit Tetraphenyldiphosphan in Tetrahydrofuran oder Schwefelkohlenstoff bereits bei -78°C unter Bildung von 1,1-Diphenyldiphosphan, (C6H5)2P—PH2 1. Gleichzeitig tritt Diphenylmonophosphan als Disproportionierungsprodukt von 1 auf. Die Umsetzung von Diphosphan mit 1,2-Diphenyldiphosphan in Tetrahydrofuran führt oberhalb von +40° zur Bildung von Monophenyldiphosphan, (C6H5)HP—PH2 2. Durch geeignete Reaktionsführung kann die Disproportionierung der Ausgangsverbindungen sowie von 2 weitgehend zurückgedrängt werden. Die angegebenen Reaktionen zur Bildung von 1 und 2 verlaufen sehr wahrscheinlich unter Ausbildung von Vierzentren-Übergangszuständen.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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