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- W4235758287 abstract "Diphosphan(4), P2H4, reagiert mit flüssigem Ammoniak im Temperaturbereich von –76 °C bis –40 °C zu einem Gemisch der Ammoniumpolyphosphide (NH4)2H2P14, (NH4)2P16, (NH4)3P19 und (NH4)3P21; daneben entsteht PH3. Das erste NMR-spektroskopisch nachweisbare Zwischenprodukt ist die bicyclische Verbindung NH4H4P7, die mit P2H4 zu den phosphorreicheren polycyclischen Phosphiden weiterreagiert. Beim Entfernen des Ammoniaks zersetzt sich das Hydrogenpolyphosphid (NH4)2H2P14 unter Bildung von PH3 und wasserstofffreien phosphorreicheren Polyphosphiden. Wird die Reaktion von Diphosphan(4) mit flüssigem Ammoniak in Gegenwart von Tetrahydrofuran durchgeführt, so entstehen als Endprodukte die Hydrogenpolyphosphide NH4H4P7 und NH4H5P8 neben PH3; als Vorstufe wurde das wasserstoffreiche, offenkettige Heptaphosphid NH4H8P7 identifiziert. Die exemplarische Untersuchung des Verhaltens von Diphosphan(4) gegenüber Aminen ergab mit dem primären Amin Ethylendiamin bei +10 °C lösungsmittelfrei oder in Gegenwart von Tetrahydrofuran die Bildung eines Polyphosphid-Gemisches aus (C2H4N2H5)2P16, (C2H4N2H5)3P21 und (C2H4N2H5)3P19 neben etwas PH3. Mit den sekundären und tertiären Aminen Diethylamin bzw. Tetramethylethylendiamin (TMEDA) fand selbst bei Raumtemperatur keine Reaktion statt. Contributions to the Chemistry of Phosphorus. 241. On the Reaction of Diphosphane(4) with Liquid Ammonia and with Amines – a New Route to Polyphosphides and Hydrogen Polyphosphides Diphosphane(4), P2H4, reacts with liquid ammonia in the temperature range –76 °C to –40 °C to furnish a mixture of the ammonium polyphosphides (NH4)2H2P14, (NH4)2P16, (NH4)3P19, and (NH4)3P21, in addition to PH3. The first intermediate product detectable by NMR spectroscopy is the bicyclic compound NH4H4P7, which reacts further with P2H4 to afford the more phosphorus-rich polycyclic phosphides. On removal of the ammonia the hydrogen polyphosphide (NH4)2H2P14 decomposes with formation of PH3 and hydrogen-free, more phosphorus-rich polyphosphides. When the reaction of diphosphane(4) with liquid ammonia is performed in the presence of tetrahydrofuran the final products are the hydrogen polyphosphides NH4H4P7 and NH4H5P8 together with PH3; the hydrogen-rich, open-chain heptaphosphide NH4H8P7 has been identified as a precursor. An investigation of the behavior of diphosphane(4) towards amines using the primary amine ethylenediamine as an example at +10 °C in the absence of a solvent or in the presence of tetrahydrofuran resulted in the formation of a polyphosphide mixture consisting of (C2H4N2H5)2P16, (C2H4N2H5)3P21, and (C2H4N2H5)3P19 as well as some PH3. No reaction occurred with the secondary and tertiary amines diethylamine and tetramethylethylenediamine (TMEDA), respectively, even at room temperature." @default.
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- W4235758287 date "1999-03-01" @default.
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- W4235758287 doi "https://doi.org/10.1002/(sici)1521-3749(199903)625:3<417::aid-zaac417>3.3.co;2-w" @default.
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