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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1685-1688 
    ISSN: 0044-2313
    Keywords: Fluorophosphanes ; Silylazides ; Phosphazenes ; N-silylated Fluorophosphazenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Reaction of Fluorophosphanes with Silylazides.The fluorophosphanes Ph2PF (1), PhOPF2 (2), C5H10NPF2 (3), (Et2N)PF2 (4), and (Et2N)2PF (5) react with Me3SiN3 via azidophosphanes R3-nP(N3)n to oligo- and polyphosphazenes, (RR′P=N)n. (iPr2N)2PF (6), however, is oxidized by Me3SiN3 yielding the N-silylated phosphazene (iPr2N)2PF=N—SiMe3 (7). tBuPh2SiN3 is considerably less reactive. On contrary to Me3SiN3 it even oxidizes 5 and 1 forming (Et2N)2FP=N—SiPh2tBu (10) and Ph2FP=N—SiPh2tBu, resp.
    Notes: Die Fluorphosphane Ph2PF (1), PhOPF2 (2), C5H10NPF2 (3), (Et2N)PF2 (4) und (Et2N)2PF (5) reagieren mit Me3SiN3 über die Zwischenstufe der Azidophosphane R3-nP(N3)n zu Oligo- und Polyphosphazenen, (RR′P=N)n. (iPr2N)2PF (6) wird dagegen durch Me3SiN3 zum N-silylierten Phosphazen (iPr2N)2PF=N—SiMe3 (7) oxidiert. tBuPh2SiN3 ist wesentlich weniger reaktiv. Im Gegensatz zu Me3SiN3 oxidiert es aber auch 5 und 1 zu (Et2N)2FP=N—SiPh2tBu (10) bzw. Ph2FP=N—SiPh2tBu.
    Additional Material: 1 Tab.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 542 (1986), S. 157-166 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of Fluoro-λ5-monophosphazenes and Fluoro-1,3-diaza-2λ5,4λ5-diphosphetidines by Means of the Staudinger Reaction35 Tetrafluoro- and 2 difluorodiaza-diphosphetidines as well as 4 difluoro- and 30 monofluoro-λ5-monophosphazenes were prepared by the Staudinger reaction between tervalent phosphorus fluorides, RnPF3-n (n = 1, 2; R = R2N, (CH2)5N, O(CH2)4N, RO, (CH2O)2, alkyl, aryl) and phenylazides, X—C6H4N3 (X = H, 4-CH3, 4-Cl, 4-Br, 4-NO2, 3-NO2). PF3 does not react with phenylazide The influence of substituents on the structure of the reaction products is discussed. Kinetic measurements allowed to determine the constants λPI of the substituents (CH2)5N, O(CH2)4N and R(C6H5)N (R = CH3, C2H5, n-C4H9).
    Notes: Durch die Umsetzung trivalenter Phosphorfluoride, RnPF3-n (n = 1, 2; R = R2N, (CH2)5N, O(CH2)4N, RO, (CH2O)2, Alkyl, Aryl) mit Phenylaziden, X—C6H4N3 (X = H, 4-CH3, 4-Cl, 4-Br, 4-NO2, 3-NO2), wurden 35 Tetrafluoro- und 2-Difluorodiazadiphosphetidine sowie 4 Difluoro- und 30 Monofluoro-α5-monophosphazene dargestellt. PF3 reagiert nicht mit Phenylazid. Der Einfluß der Substituenten auf die Konstitution der Reaktionsprodukte wird diskutiert. Kinetische Messungen ermöglichten die Bestimmung der Substituentenkonstanten σPI für (CH2)5N, O(CH2)4N und R(C6H5)N (R = CH3, C2H5, n-C4H9).
    Additional Material: 6 Tab.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 544 (1987), S. 225-231 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: N.M.R. Investigations of Fluorodiazadiphosphetidines and Fluoro-λ5-monophosphazenesThe 19F and 31P n.m.r. data of 37 fluorodiazadiphosphetidines [RR′PF—NC6H4X]2, and 62 fluoro-λ5-monophosphazenes, RR′PF=NC6H4X, are submitted. In the case of tetrafluorodiazadiphosphetidines, [RPF2—NC6H4X]2, an intramolecular exchange of the fluorine atoms at phosphorus has to be concluded from the n.m.r. data. The influence of the substituents R and X on the n.m.r. parameters is discussed using simple models of molecular structure.
    Notes: Es werden die 19F- und 31P-NMR-Daten von 37 Fluorodiazadiphosphetidinen, [RR′PF—NC6H4X]2, und 62 Fluoro-λ5-monophosphazenen, RR′PF=NC6H4X, mitgeteilt. Aus ihnen muß für die Tetrafluorodiazadiphosphetidine, [RPF2—NC6H4X]2, auf einen intramolekularen Positionswechsel der Fluoratome am Phosphor geschlossen werden. Der Einfluß der Substituenten R und X auf die NMR-Parameter wird anhand einfacher Modelle der Molekülstruktur diskutiert.
    Additional Material: 1 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 539 (1986), S. 183-186 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations on the Oxidation of N-Alkyl-bis(difluoro-phosphorus(III))amidesOxidation of RN(PF2)2 by N2O4 in n-hexane leads to bis(difluorophosphoryl)amides, RN(POF2)2 (R = Me, Et), in good yields. Only one phosphorus atom is oxidized by phenylazide resulting in the formation of 1.3-diphenyl-2.4-bis(difluorophosphorus(III)-N-alkyl-amido)-2.2.4.4-tetrafluoro-diaza-λ5,λ5 diphosphetidines, [F2P—N(R)—PF2NPh]2.
    Notes: Die Oxydation von RN(PF2)2 mit N2O4 in n-Hexan führt in guten Ausbeuten zu den Bis(difluorophosphoryl)-amiden RN(POF2)2 (R = Me, Et). Mit Phenylazid wird nur ein Phosphoratom oxydiert und es werden 1,3-Diphenyl-2,4-bis(difluorophosphor(III)-N-alkylamido)-2,2,4,4-tetrafluoro-diaza-λ5,λ5-diphosphetidine, [F2P—N(R)—PF2NPh]2, erhalten.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 539 (1986), S. 187-190 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of N-Alkyl-bis(difluorophosphoryl)amides, RN(POF2)2, with Silylated Nucleophiles and Et2NSF3N-Alkyl-bis(difluorophosphoryl)amides, RN(POF2)2 (R = Me, Et), react in any case with silylated nucleophiles such as Me3SiOMe and Me3SiNEt2 under cleavage of the PNP bridge forming derivatives of di- and monofluorophosphoric acid. In their reaction with Et2NSF3 (RNPF3)2 and OPF3 or PF5, resp., are obtained. The compounds F2P(O)—NR—PF4 and RN(PF4)2 postulated as intermediates are not stable.
    Notes: N-Alkyl-bis(difluorophosphoryl)amide, RN(POF2)2 (R = Me, Et), reagieren mit den silylierten Nukleophilen Me3SiOMe und Me3SiNEt2 in jedem Fall unter Spaltung der PNP-Brücke zu Di- und Monofluorophosphorsäurederivaten. Bei der Reaktion mit Et2NSF3 werden OPF3 bzw. PF5 und (RNPF3)2 erhalten. Die als Zwischenprodukte angenommenen Verbindungen F2P(O)—NR—PF4 und RN(PF4)2 sind nicht stabil.
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