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  • Chemistry  (18)
  • Imidodiphosphoryl Compounds
  • Methanediphosphonic Acid Derivatives
  • Fluoro(organyl)phosphanes
  • Halomethylphosphonium Halides
  • 1985-1989  (16)
  • 1970-1974  (2)
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Keywords
  • Chemistry  (18)
  • Imidodiphosphoryl Compounds
  • Methanediphosphonic Acid Derivatives
  • Fluoro(organyl)phosphanes
  • Halomethylphosphonium Halides
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 531 (1985), S. 73-81 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of the Two-component Systems P(OR)3 - x(NR2)x (x = 0-3)/CCl4 and P4/CCl4 with HF-DonatorsThe combination of organylammonium fluorides and carbon tetrachloride is a good agent for oxidative fluorination of trivalent phosphorus compounds. As oxidation products [(RO)PF5]- and (RO)2P(O)F are obtained from P(OR)3, (Et2N)2P(O)F and (Et2N)2(EtO)PF2 from P(OEt)(NEt2)2 as well as (Et2N)3PF2 and [(Et2N)3PF]+ from P(NEt2)3. In the system R2NH/CCl4/Et3N · n HF P4 is fast oxidized forming [HPF5]-, R2NH · PF5 and (R2N)2P(O)F. In the case of simultaneous addition of alcohols [(RO)PF5]-, (RO)3PO and (R2N)2P(O)F are formed. The reactions are controlled by the nucleophilic power and the concentration of fluoride, the acidity of the system, and the temperature.
    Notes: Die Kombination von Organylammoniumfluoriden mit Tetrachlorkohlenstoff stellt ein gutes Agens zur oxydativen Fluorierung von trivalenten Phosphorverbindungen dar. Aus P(OR)3 werden als Oxydationsprodukte [(RO)PF5]- und (RO)2P(O)F, aus P(OEt)(NEt2)2 (Et2N)2P(O)F und (Et2N)2(EtO)PF2 und aus P(NEt2)3 (Et2N)3PF2 und [(Et2N)3PF]+ erhalten. P4 wird im System R2NH/CCl4/Et3N · n HF in kurzer Zeit zu [HPF5]-, R2NH · PF5 und (R2N)2P(O)F abgebaut. Bei gleichzeitigem Alkoholzusatz entstehen [(RO)PF5]-, (RO)3PO und (R2N)2P(O)F. Die Reaktionen sind über die Nukleophilie und Konzentration der Fluoridionen, die Acidität der Systeme und die Temperatur steuerbar.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 530 (1985), S. 207-212 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Properties of Pentafluorophosphates, YPF5- (Y = OR, NHAr), and PF5-Amine Adducts, PF5 · NHR2In the presence of secondary amines instead of hexafluorophosphates, PF6-, PF5-amine adducts, PF5 · NHR2, are obtained by the reaction of PCl5 with alkylammonium fluorides in acetonitrile.The additional presence of alcohols or phenol leads to the formation of alkoxy- or aroxypentafluorophosphates, ROPF5-. The PF5-amine adducts can be converted into ROPF5- or arylimidopentafluorophosphates, ArNHPF5-, resp., by treating with alcohols or aryl amines, resp.
    Notes: Bei der Umsetzung von PCl5 mit Alkylammoniumfluoriden in Acetonitril werden in Gegenwart sec. Amine anstelle von Hexafluorophosphaten, PF6-, PF5-Amin-Addukte, PF5 · HNR2, und bei zusätzlicher Anwesenheit von Alkoholen bzw. Phenol, Alkoxy- bzw. Aroxypentafluorophosphate, ROPF5-, erhalten. Die PF5-Amin-Addukte setzen sich mit Alkoholen oder Arylaminen zu ROPF5- bzw. Arylimidopentafluorophosphaten, ArNHPF5-, um.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 404 (1974), S. 219-224 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Properties of Imidodiphosphoric Acid AmidesTrichlorophosphazene phosphoryldichloride, Cl3P=N—P(O)Cl2, reacts with the stoichiometric amount of anhydrous formic acid resulting the tetrachloride of the imidodiphosphoric acid, Cl2(O)P—NH—P(O)Cl2. This tetrachloride yields with diazomethane the N-methyl compound, Cl2(O)P—N(CH3)—P(O)Cl2. The tetramide of the imidodiphosphoric acid and its octalkyl derivatives are obtained by reaction of the tetrachloride with ammonia, dimethylamine, and diethylamine, respectively.
    Notes: Trichlorphazenphosphoryldichlorid, Cl3P=N—P(O)Cl2, reagiert mit der stöchiometrischen Menge wasserfreier Ameisensäure zum Imidodiphosphorsäuretetrachlorid, Cl2(O)P—NH—P(O)Cl2. Mit Diazomethan bildet dieses das N-Methylderivat, Cl2(O)P—N(CH3)—P(O)Cl2. Durch Umsetzung mit Ammoniak, Dimethyl- bzw. Diäthylamin werden das Imidodiphosphorsäuretetramid sowie die entsprechenden Octaalkylderivate erhalten.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 523 (1985), S. 180-186 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of the Two-component System Trialkylphosphite/Carbon Tetrachloride with Nucleophiles Containing Hydrogen. 2. Reaction with Ammonia and AminesAmmonia and primary amines react with the two-component system trialkylphosphite/carbon tetrachloride yielding diester-amides of phosphoric acid, (RO)2P(O)NHR′. If an excess of amine is used compounds of the type ROP(O)(NHR′)2 and OP(NHR′)3 are formed too. By the reaction of (RO)3P/CCl4 in presence of secondary and tertiary amines the first reaction product is (RO)2P(O)CCl3 which yields with the amine [NRR′R″R″′]+[Cl3CP(OR)O2]-; (R = Et, Bu).
    Notes: Ammoniak und primäre Amine reagieren mit dem Zweikomponenten-system Trialkylphosphit/Tetrachlokohlenstoff zu Diesteramiden der Phosphorsäure, (RO)2P(O)NHR′. Bei Aminüberschuß werden auch Verbindungen des Typs ROP(O)(NHR′)2 und OP(NHR′)3 gebildet. Bei der Reaktion von (RO)3P/CCl4 in Gegenwart sekundärer und tertiärer Amine entsteht zunächst (RO)2 P(O)CCl3, das mit dem Amin zu [NRR′R″R′]+[Cl3CP(OR)O2]- reagiert; (R = Et, Bu).
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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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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 405 (1974), S. 109-112 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of Imidodiphosphoryl Tetrachloride with Phosphorus PentachlorideImidodiphosphoryl tetrachloride quantitatively reacts with PCl5 to form, HCl, POCl3, and Cl3P=N—POCl2. The mechanism of the reaction is discussed. Using 32P-labeled PCl5 was proved that the attack of the PCl5 to imidodiphosphoryl tetrachloride does occur about an oxygen atom.
    Notes: Imidodiphosphoryltetrachlorid reagiert mit PCl5 quantitativ zu HCl, POCl3 und Cl3P=N—POCl2. Der mögliche Reaktionsmechanismus wird diskutiert. Mit 32P-markiertem PCl5 gelang der Nachweis, daß der Angriff des PCl5 am Imidodiphosphoryltetrachlorid über ein Sauerstoffatom erfolgt.
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  • 7
    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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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 563 (1988), S. 167-172 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Tetraphenyl Imidodiphosphate as Ligand in Fluoro Complexes. 1. Fluoro Complexes of TitaniumIn acetonitrile TiF4 reacts with tetraphenyl imidodiphosphate forming two tetrafluoro (I, II) and three trifluoro complexes (III, IV, V) as well as one difluorotitanium complex (VI). The difluoro complex VI is exclusively formed by sing an excess of the ligand. VI was isolated and analytically characterized. The constitution and configuration of the complexes are concluded from 19F and 31P n.m.r. data. The tetraphenyl imidodiphosphate is only bidentately bonded, i.e. as chelate or bridging ligand; in the substitution complexes III-VI it is coordinated as anion.
    Notes: TiF4 bildet mit Imidodiphosphorsäuretetraphenylester in CH3CN zwei Tetrafluoro- (I, II) und drei Trifluorokomplexe (III, IV, V) sowie einen Difluorotitan-Komplex (VI). Mit Ligandenüberschuß entsteht ausschließlich der Difluorokomplex, der isoliert und elementar-analytisch charakterisiert wurde. Die Konstitutions- und Konfigurationsaussagen zu den übrigen Komplexen basieren auf 19F- und 31P-NMR-Untersuchungen. Der Imidodiphosphorsäureestr ist in den Komplexen stets zweizähnig als Chelat- oder Brückenligand gebunden; in den Substitutions-komplexen III-VI ist er in seiner anionischen Form enthalten.
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  • 9
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of Diphenylfluorophosphane with Aldehydes. Crystal Structure of [α-(Difluorodiphenyl-λ5-phosphanyl)] Piperonyl DiphenylphosphiniteDiphenylfluorophosphane, Ph2PF, reacts with aldehydes forming phosphinito phosphoranes, Ph2F2P—CHR—O—PPh2. [α-(Difluorodiphenyl-λ5-phosphanyl)] piperonyl diphenyl-phosphinite, obtained by the reaction of Ph2PF with piperonal, crystallizes in the triclinic space group P1 with a = 969.3 pm, b = 2360 pm, c = 607,3 pm, α = 88.33°, β = 102.79°, γ = 92.40° and Z = 2.
    Notes: Diphenylfluorphosphan, Ph2PF, reagiert mit Aldehyden unter Bildung von Phosphinitophosphoranen, Ph2F2P—CHR—O—PPh2. Der mit Piperonal erhaltene Diphenyl-phosphinigsäure-[α-(difluorodiphenyl-λ5-phosphanyl)]piperonylestr kristallisiert in der triklinen Raumgruppe P1 mit a = 969,3 pm, b = 2360 pm, c = 607,3 pm, α = 88,33°, β = 102,79°, γ = 92,40° und Z = 2.
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  • 10
    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).
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