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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 3214-3216 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2380-2388 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On 2-tert-Butyl-l,3,2λ5-dioxaphospholanes and 2-tert-Butyl-1,2λ5-oxaphosphetanesOxidative addition of hexafluoroacetone to the phosphorus(III) compounds 1c-g furnished the 1,3,2λ5-dioxaphospholanes 2c, 2d, 2f, 2g, and the 1,2λ5-oxaphosphetane 3, respectively; 2d undergoes thermal rearrangement to the corresponding l,2λ5-oxaphosphetane 4. The phospholes 5 and 6 are formed from hexafluorobiacetyl with phosphinous acid esters. 19F NMR spectroscopy was employed to investigate dynamic effects in the compounds obtained. For the phosphorane 2 c magnetic nonequivalence of the CF3 groups of the dioxaphospholane ring system as well as of those of the (CF3)2CHO group was observed. The related compounds 7-9 were studied for comparison, and the influence of the bulky tert-butyl groups at phosphorus was investigated.
    Notes: Durch oxidative Addition von Hexafluoraceton an die Phosphor(III)-Verbindungen 1c-g werden die 1,3,2λ5-Dioxaphospholane 2c, 2d, 2f und 2g bzw. das 1,2λ5-Oxaphosphetan 3 gebildet; 2d lagert sich thermisch in das entsprechende 1,2λ5-Oxaphosphetan 4 um. Die Phosphole 5 und 6 entstehen aus Hexafluorbiacetyl und Phosphinigsäureestern. Mit Hilfe der 19 F-NMR-Spektroskopie wurden dynamische Effekte untersucht. Bei dem Phosphoran 2c tritt magnetische Nichtäquivalenz sowohl der CF3-Gruppen des Dioxaphospholan-Ringsystems als auch der des (CF3)2CHO-Restes auf. Die analogen Verbindungen 7-9 wurden zur vergleichenden Betrachtung herangezogen und der Einfluß der raumerfüllenden tert-Butylgruppe am Phosphor studiert.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 3105-3111 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of an N-Silylated Iminophosphine (Phospha(III)azene) with Perfluorinated KetonesCycloaddition of hexafluoroacetone to the iminophosphine 4 furnishes the novel three-membered ring compound 2, the first isolable product of this type involving a main group element. 4 reacts with perfluorobiacetyl to form the 4,5-bis(trifluoromethyl)-1,3,2λ5-dioxaphosphole 8. The analogous 4,4,5,5-tetrakis(trifluoromethyl)-1,3,2λ5-dioxaphospholane 1a is obtained in the reaction of lithium bis(trimethylsilyl)amide with the phospholane 3. The product resulting from dimerisation of 4, compound 5, is found to oxidatively add only one molecule of perfluorobiacetyl with formation of the λ3λ5-diazadiphosphetidine 9.
    Notes: Das erste isolierbare Dreiringsystem 2, das Hexafluoraceton mit einem Hauptgruppenelement bildet, konnte durch 1,2-Cycloaddition an das Iminophosphin 4 dargestellt werden. Perfluorbiacetyl ergibt das 4,5-Bis(trifluormethyl)-1,3,2λ5-dioxaphosphol 8. Das analoge 4,4,5,5-Tetrakis(trifluormethyl)-1,3,2λ5-dioxaphospholan 1a wurde durch Umsetzung von Lithium-bis(trimethylsilyl)amid mit dem Phospholan 3 synthetisiert. Das Dimere von 4, Verbindung 5, addiert nur ein Molekül Perfluorbiacetyl unter Bildung des λ3λ5-Diazadiphosphetidins 9.
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