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  • Chemistry  (19)
  • Methanediphosphonic Acid Derivatives  (1)
  • Fluoro(organyl)phosphanes
  • Halomethylphosphonium Halides
  • 1995-1999  (3)
  • 1985-1989  (16)
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 865-870 
    ISSN: 0044-2313
    Keywords: Fluoridolysis ; N-Phosphoryl Phosphazenes ; Fluorophosphates ; Diazadiphosphetine ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Fluoridolysis of N-Phosphoryl PhosphazenesIn the reaction of the N-phosphoryl phosphazenes X3P=N—P(Y)X2 (X = Cl, PhO, Et2N, CF3CH2O, PrS, Ph; Y = O, S) (1-18) with Et3N · nHF (n ≍ 3 or 0.6) fluoro derivatives of N-phosphoryl phosphazenes (see table 2) as well as N-phosphorylated imiddotetrafluorophosphates, [F4P=N—P(Y)Cl2]- (Y = O, S), and imidopentafluorophosphates, [F5P—N—P(Y)X2]2- or [F5P—NH—P(O)X2]- (see table 3), are formed. t-BuNHPCl2=N—POCl2 reacts in acetonitrile with Et3N or i-Pr2EtN to form a product, representing probably the diazadiphosphetine (5 b).
    Notes: Bei der Umsetzung der N-Phosphorylphosphazene X3P=N—P(Y)X2 (X = Cl, PhO, Et2N, CF3CH2O, PrS, Ph; Y = O, S) (1-18) mit Et3N · nHF (n ≍ 3 oder 0,6) werden durch den Austausch von Chlor sowie PhO-, Et2N- und CF3CH2O-Gruppen gegen Fluor Fluorderivate von N-Phosphorylphosphazenen (siehe Tab. 2) sowie N-phosphorylierte Imiddotetra- und -pentafluorophosphate, [F4P=N—P(Y)Cl2]- (Y = O, S) und [F5P—N—P(Y)X2]2- bzw. [F5P—NH—P(O)X2]- (siehe Tab. 3) gebildet. t-BuNHPCl2=N—POCl2 reagiert in Acetonitril mit Et3N oder i-Pr2EtN zu einem Produkt, bei dem es sich höchstwahrscheinlich um das Diazadiphosphetin (5 b) handelt.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 901-903 
    ISSN: 0044-2313
    Keywords: Fluoridolysis ; Cyclophosphazenes ; Polyphosphazenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Fluoridolysis of Cyclophosphazenes and Lineary PolyphosphazenesThe fluorination of nongeminal trans P3N3Cl4(NEt2)2 and nongeminal trans P3N3Cl3(NEt2)3 with the fluorination agent Et3N · 0,6 HF (B) occurs under retention of configuration yielding P3N3Cl2F2(NEt2)2 and P3N3F4(NEt2)2 or P3N3F3(NEt2)3, respectively. P3N3Cl6 is nearly quantitatively converted into P3N3F6. Poly(dichlorophosphazene) reacts to a poly(difluorophosphazene), (PNF2)n, distinguished by a moderate solubility in THF.
    Notes: Die Fluorierung von nichtgeminalem trans-P3N3Cl4(NEt2)2 und nichtgeminalem trans-P3N3Cl3(NEt2)3 mit dem Fluorierungsagens Et3N · 0,6 HF (B) verläuft unter Erhalt der Konfiguration zu P3N3Cl2F2(NEt2)2 und P3N3F4(NEt2)2 bzw. P3N3F3(NEt2)3. P3N3Cl6 wird nahezu vollständig in P3N3F6 überführt. Poly(dichlorphosphazen) reagiert zu einem THF-löslichen Poly(difluorphosphazen), (PNF2)n.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 894-900 
    ISSN: 0044-2313
    Keywords: Fluoridolysis ; Imidodiphosphoryl Compounds ; Methanediphosphonic Acid Derivatives ; Azadiphosphetidine ; Pentafluorophosphates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Fluoridolysis of Diphosphoryl CompoundsThe behaviour of diphosphoryl compounds [X2(O)P]2Y in fluoridolysis reactions is decisively determined by the nature of the bridging group Y. In the cases of Y = NH and CH2 and X = Cl [F2P(O)]2N- and [F2P(O)]2CH2 are obtained quantitatively. For Y = NPh, O, and CH2 the formation of phosphorylated pentafluorophosphates [F5P—Y—POX2]- is observed. Amido and ester derivatives containing fluorine (see table 2) are obtained from the corresponding chloro compounds by Cl/F exchange. Fluoridolysis of the azadiphosphetidine 19 results in the formation of acyclic 19 a.
    Notes: Das Fluoridolyseverhalten von Diphosphorylverbindungen [X2(O)P]2Y wird maßgeblich durch die Brückengruppe Y bestimmt. Im Falle von Y = NH und CH2 sowie X = Cl werden quantitativ [F2P(O)]2N- und [F2P(O)]2CH2 erhalten. Für Y = NPh, O und CH2 wird die Bildung von phosphorylierten Pentafluorophosphaten [F5P—Y—POX2]- beobachtet. Aus chlorhaltigen Amido- und Esterderivaten werden durch Chlor-Fluor-Austausch die entsprechenden Fluorderivate erhalten (siehe Tab. 2). Die Fluoridolyse des Azadiphosphetidins 19 ergibt die acyclische Verbindung 19 a.
    Additional Material: 5 Tab.
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  • 4
    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.
    Additional Material: 1 Tab.
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  • 5
    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.
    Additional Material: 2 Ill.
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  • 6
    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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  • 7
    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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  • 8
    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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  • 9
    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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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 547 (1987), S. 216-224 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Experimental Investigations on the Tungsten Transport in Systems Containing Fluorine CompoundsInformation on the chemical processes in tungsten incandescent lamps containing gaseous fluorides are obtained by i.r. and u.v. spectroscopic and mass spectrometric analysis of the gasphase as well as by investigating the deposits at the wall and the changes at the filament. Due to the involvement of the wall in the reaction fluorine carrier gases are converted irreversibly into SiF4 which also maintains the chemical tungsten transport. In systems containing fluorine and bromine silicon bromide fluorides are formed.
    Notes: Durch die IR- und UV-spektroskopische sowie massenspektrometrische Analyse der Gasphase sowie die Untersuchung gebildeter Beläge und der Veränderungen am Glühkörper werden Aussagen über die chemischen Vorgänge in Wolframlampen mit fluorhaltigen Füllgasen erhalten. Fluorträgergase werden in der brennenden Lampe durch die Einbeziehung der Wand in das Reaktionsgeschehen irreversibel in SiF4 umgewandelt, das selbst transportaktiv ist. In Fluor und Brom enthaltenden Systemen werden Siliciumbromidfluoride, SiBr4-xFx, gebildet.
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