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  • Chemistry  (16)
  • Methanediphosphonic Acid Derivatives
  • Fluoro(organyl)phosphanes
  • Halomethylphosphonium Halides
  • 1985-1989  (16)
Collection
Keywords
  • Chemistry  (16)
  • Methanediphosphonic Acid Derivatives
  • Fluoro(organyl)phosphanes
  • Halomethylphosphonium Halides
  • Inorganic Chemistry  (16)
Publisher
Years
Year
  • 1
    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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  • 2
    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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  • 3
    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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  • 4
    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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  • 5
    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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  • 6
    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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  • 7
    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.
    Additional Material: 2 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 551 (1987), S. 223-230 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of CF4, CBrF3, and CBr2F2 with SilicaCF4 reacts with silica above 1200 K forming SiF4 and CO2. CBrF3 and CBr2F2 yield SiF4, Br2, CO2, and CO as well as products of pyrolysis, such as C2BrF5, C2Br2F4, and others. The reaction starts at 900 K (CBrF3) or 700 K (CBr2F2), resp. The CO2/CO ratio is higher than expected. SiF4 is absorbed at the surface of silica to a considerable extent.
    Notes: CF4 reagiert mit Kieselglas oberhalb 1200 K unter Bildung von SiF4 und CO2. CBrF3 und CBr2F2 ergeben SiF4, Br2, CO2 sowie CO und zwischenzeitlich als Pyrolyseprodukte unter anderen C2BrF5 und C2Br2F4. Die Reaktion beginnt bei 900 K (CBrF3) bzw. bei 700 K (CBr2F2). Das CO2/CO-Verhältnis ist höher als erwartet. SiF4 wird an der Oberfläche des Kieselglases in beträchtlichem Umfang absorbiert.
    Additional Material: 2 Ill.
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  • 9
    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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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 547 (1987), S. 205-215 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thermodynamic Calculations on the Transport of Tungsten in Systems Containing Fluorine CompoundsInformation on the transport behaviour of tungsten in systems containing fluorine is obtained by a thermodynamic analysis of the systems W(s)-F, W(s)-F-O, W(s)-F-Br, W(s)-F-Br-O, W(s)-Si-F, W(s)-B-F, W(s)-Si-F-Br, and W(s)-B-F-Br. The results are compared with experimental findings. The influence of bromine, oxygen, silicon, and boron on the transport of tungsten is investigated. The nonblackening condition (dλW/dT 〈 0) is fulfilled in systems containing fluorine as well as bromine.
    Notes: Durch eine thermodynamische Analyse der Systeme W(s)-F, W(s)-F-O, W(s)-F-Br, W(s)-F-Br-O, W(s)-Si-F, W(s)-B-F, W(s)-Si-F-Br und W(s)-B-F-Br werden Aussagen zum Transportverhalten von Wolfram in fluorhaltigen Systemen erhalten und mit experimentellen Befunden verglichen. Der Einfluß von Brom, Sauerstoff, Silizium und Bor auf den Wolframtransport wird untersucht. Die Nichtschwärzungsbedingung (dλW/dT 〈 0) ist in fluor- und bromhaltigen Systemen erfüllt.
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