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  • 1
    ISSN: 0044-2313
    Keywords: Diphosphete ; Phosphorus-Ylid-Iminophosphoranes ; Syntheses ; NMR, IR, Mass Spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of 1,1,3,3-Tetrakis(dimethylamino)-1λ5,3λ5-diphosphete with N—H and P—H Acidic Compounds1,1,3,3-Tetrakis(dimethylamino)-1λ5,3λ5-diphosphete, 1, reacts with aniline to give by opening of the ring 2,2,4,4-tetrakis(dimethylamino)-1-phenyl-1,2λ5,4λ5-azadiphosphapenta-1,3-diene, 2, with p-CN—C6F4—NH2 the product is 1-(4-cyano-2,3,5,6-tetrafluorophenyl)-2,2,4,4-tetrakis(dimethylamino)-1,2λ5,4λ5-azadiphosphapenta-1,3-diene, 3. t-Butylamine or diethylamine do not react with 1. Mesitylphosphane opens the ring system 1 forming by reduction of one phosphorus atom {[bis(dimethylamino)phosphanyl]methylidene}bis(dimethylamino)methylphosphorane, 4. The same product 4 is obtained by reaction with phenylphosphane. The reaction products 2-4 are characterized by their nmr, mass, and ir spectra. Their way of formation is discussed. In 4 a 5J(PH), in 3 a 7J(CF) long range coupling constant could be identified.
    Notes: 1,1,3,3-Tetrakis(dimethylamino)-1λ5,3λ5-diphosphet, 1, reagiert mit Anilin unter Ringöffnung zu 2,2,4,4-Tetrakis(dimethylamino)-1-phenyl-1,2λ5,4λ5-azadiphosphapenta-1,3-dien, 2, mit p-CN—C6F4—NH2 zu 1-(4-Cyan-2,3,5,6-tetrafluorphenyl)-2,2,4,4-tetrakis(dimethylamino)-1,2λ5,4λ5-azadiphosphapenta-1,3-dien, 3. t-Butylamin oder Diethylamin reagieren nicht mit 1. Mesitylphosphan öffnet das Ringsystem 1 und bildet unter Reduktion eines Phosphoratoms {[Bis(dimethylamino)phosphanyl]methyliden}bis(dimethylamino)methylphosphoran 4. Das gleiche Produkt 4 liefert auch die Umsetzung mit Phenylphosphan. Die Reaktionsprodukte 2-4 sind durch ihre NMR-, Massen- und IR-Spektren charakterisiert. Ihr Bildungsweg wird diskutiert. Bei 4 kann eine 5J(PH)- und bei 3 eine 7J(CF)-long-range-Kopplungskonstante nachgewiesen werden.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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