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  • 1
    ISSN: 0022-1139
    Keywords: Aryl(trifluoromethyl)bismuth compounds ; Benzoylpyridinium chloride ; Inductive parameters ; Metathesis reactions ; NMR spectroscopy ; Resonance parameters ; Synthesis
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0044-2313
    Keywords: Xenon-oxo compounds ; 129Xe n.m.r. study ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Lewis-Acid Initiated Syntheses of Xenon-Oxo Compounds - a 129Xe-NMR StudyThe reaction of XeF2 with B(OR)3 yield FXeOR (R: SO2CF3) and Xe(OR)2 (R: COCF3), respectively. In the second case the intermediate formation of FXeOCOCF3 is detectable. In a solution of XeF2 and BF3 · O(CH3)2 in CD3CN the cation [FXe.NCCD3]+ can be observed. The syntheses of FXeOR (R: SO2CF3, SO2C4F9) and Xe(OR)2 (R:COCF3, COC2F5) also succeed in the reaction of XeF2 with the corresponding alkali metal sulfonates and carboxylates in the presence of BF3 · O(CH3)2. Due to the 129Xe-NMR spectra the mechanism of formation and the bond types of these partly new derivatives are discussed.
    Notes: Bei den Reaktionen von XeF2 mit B(OR)3 entstehen FXeOR (R: SO2CF3) bzw. Xe(OR)2 (R:COCF3); dabei ist auch die intermediäre Bildung von FXeOCOCF3 nachweisbar. In einer Lösung von Xef2 und BF3 · O(CH3)2 in CD3CN wird das Vorliegen von [FXe · NCCD3]+ beobachtet. Die Synthesen von FXeOR (R: SO2CF3, SO2C4F9) sowie Xe(OR)2 (R:COCF3,COC2F5) gelingen ebenfalls durch die Umsetzungen von XeF2 mit den entsprechenden Alkalimetallsulfonaten bzw. -carboxylaten in Gegenwart von BF3 · O(CH3)2. Anhand der129Xe-NMR Spektren werden die Bildungsmechanismen und die Bindungsverhältnisse dieser teilweise neuen Xenonderivate diskutiert.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 122-128 
    ISSN: 0044-2313
    Keywords: tris(2,6-difluorophenyl)bismuth dihalides ; tris(2,6-difluorophenyl)bismuth bis(trifluoromethanesulfonate) ; tris(2,6-difluorophenyl)bismuth bis(trifluoroacetate) ; 2,6-difluorophenyliodine tetrafluoride ; synthesis ; NMR ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Properties and Reactions of Tris(2,6-difluorophenyl)bismuth(III) and Tris(2,6-difluorophenyl)bismuth(V) Derivatives(2,6-F2C6H3)3BiF2 and (2,6-F2C6H3)3BiCl2 are prepared oxidizing (2,6-F2C6H3)3Bi with XeF2 or Cl2 respectively, while direct fluorination effect the oxidation of the aromatic system. The reaction of (2,6-F2C6H3)3BiCl2 With (CH3)3SiCl yields (2,6-F2C6H3)3BiCl2. Attempts to oxidize (2,6-F2C6H3)3Bi with Br2, I2 and ICl give (2,6-F2C6H3)X and BiX′3 (X = Br, I; X′ = Cl, Br, I). The rection of (2,6-F2C6H3)3Bi with IF5 gives BiF3 and (2,6-F2C6H3)IF4. (2,6-F2C6H3)3Bi(OCOCF3)2 and (2,6-F2C6H3)3Bi(OSO2CF3)2 are formed via ligand exchange rection of (2,6-F2C6H3)3BiF2 with (CH3)3SiOR or of (2,6-F2C6H3)3BiCl2 with AgOR (R = COCF3, SO2CF3). The preparations and properties of the new compounds are described. (2,6-F2C6H3)3Sb and (2,6-F2C6H3)2Te are prepared by the transmetalation reactions of (2,6-F2C6H3)3Bi with Sb and Te.
    Notes: (2,6-F2C6H3)3 BiF2und(2,6-F2C6H3)3BiCl2 werden durch Oxidation von (2,6-F2C6H3)3 Bi mit XeF2 bzw. Cl2 dargestellt, während die Direktfluorierung zu einer Oxidation des aromatischen Systems führt, (2,6-F2C6H3)3BiCl2 wird auch durch die Umsetzung von (2,6-F2C6H3)3 BiF2 mit (CH3)3SiCl erhalten. Oxidationsversuche von (2,6-F2C6H3)3Bi mit Br2, I2 und ICl ergeben (2,6-F2C6H3)X und BiX′3 (X = Br, I; X′ = Cl, Br, I). Die Umsetzung von (2,6-F2C6H3)3Bi mit IF5 führt zur Bildung von BiF3 und (2,6-F2C6H3)IF4. (2,6-F2C6H3)3Bi(OCOCF3)2 bzw. (2,6-F2C6H3)3Bi(OSO2CF3)2 werden durch Ligandenaustauschreaktionen von (2,6-F2C6H3)3BiF2 mit (CH3)3SiOR oder von (2,6-F2C6H3)3BiCl2 mit AgOR gebildet (R COCF3, SO2CF3). Die Syntheseverfahren und Eigenschaften der neuen Verbindungen werden beschrieben. Durch Transmetallierungsreaktionen von (2,6-F2C6H3)3Bi mit Te und Sb werden (2,6-F2C6H3)3Sb und (2,6-F2C6H3)2Te dargestellt.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0044-2313
    Keywords: Tris(fluorophenyl)antimony and -bismuth compounds ; bismuth tris(2,6-difluorobenzoate) ; preparations ; crystal structure of tris(2,6-difluorophenyl)bismuth ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses and Properties of Some New Tris(fluorophenyl)antimony and -bismuth Compounds. Crystal Structure of Tris(2,6-difluorophenyl)bismuth(2,6-F2C6H3)3Bi, (2,4,6-F3C6H2)3Bi, and (2,6-F2C6H3)3Sb are prepared via Grignard reactions with BiBr3 and SbBr3, respectively. The syntheses and properties of the new compounds and the crystal structure of (2,6-F2C6H3)3Bi are described. From the reaction of BiBr3 with Ag(OCOC6H3F2) the bismuth benzoate Bi(OCOC6H3F2)3 is formed in 83% yield. Attempts to prepare (2,6-F2C6H3)3Bi by decarboxylation of the bismuth benzoate failed.
    Notes: (2,6-F2C6H3)3Bi, (2,4,6-F3C6H2)3Bi und (2,6-F2C6H3)3Sb werden durch Grignard-Reaktionen mit BiBr3 bzw. SbBr3 dargestellt. Die Synthesebedingungen und die Eigenschaften der neuen Verbindungen sowie die Kristallstruktur von (2,6-F2C6H3)3Bi werden beschrieben. Bi(OCOC6H3F2)3 entsteht in 83% Ausbeute aus BiBr3 und Ag(OCOC6H3F2); die präparative Darstellung von (2,6-F2C6H3)3Bi durch Decarboxylierung des Bismutbenzoats gelingt nicht.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0044-2313
    Keywords: Arylxenon trifluoromethanesulfonates ; electrophilic aromatic substitution ; xenontrifluoroacetate trifluoromethanesulfonate ; NMR spectra ; X-ray crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Die direkte Synthese von Arylxenontrifluormethansulfonaten durch elektrophile SubstitutionBei der Reaktion von Xenonbis(trifluoracetat) mit Trifluormethansulfonsäure wird die neue, hochreaktive, unsymmetrische Xenon-Sauerstoff-Verbindung CF3COOXeOSO2CF3 erzeugt. Benzolderivate mit elektronenziehenden Substituenten wie F, CF3, Cl und NO2 werden von diesem Intermediat unter Bildung von Arylxenontrifluormethansulfonaten elektrophil angegriffen. Über diese Eintopfsynthese wurden Trifluormethansulfonate mit den Kationen [Xe(2,4,6-F3C6H2)]+, [Xe(2-F-5-NO2C6H3)]+, [Xe(2-F-5-CF3C6H3)]+ und [Xe(3,5-(CF3)2C6H3)]+ synthetisiert. Alle Verbindungen wurden durch ihre NMR-, Massen- und Schwingungsspektren charakterisiert.Zusätzlich wurden mehrere neue Arylxenontrifluormethansulfonate als Produkte der Umsetzungen von 1,3-F2C6H4 und weiteren desaktivierten Benzolen mit Xenon(trifluoracetat)trifluormethansulfonat anhand der 129Xe-NMR-Spektren identifiziert.Fluorsubstituenten in ortho-Position zu Xenon erhöhen signifikant die thermische Stabilität der Arylxenontrifluormethansulfonate.Die Molekülstruktur von [Xe(2,6-F2C6H3)][OSO2CF3] wurde durch eine Einkristallröntgenstrukturanalyse bestimmt. Die Arylxenoneinheit koordiniert schwach mit einem Sauerstoffatom des CF3SO3-Anions. Die Verbindung kristallisiert in der triklinen Raumgruppe mit a = 880.9(3) pm, b = 1093.9(5) pm, c = 1209.8(5) pm, α = 89.04(4)°, β = 74.23(3)°, γ = 86.03(3)°, Z = 4.
    Notes: The reaction of xenonbis(trifluoroacetate) and trifluoromethanesulfonic acid (triflic acid) gave the new, highly reactive unsymmetrical xenon-oxo species CF3COOXeOSO2CF3. Benzene derivates, containing electron withdrawing substituents such as -F, -CF3, -Cl or -NO2 were electrophilic attacked by this intermediate to yield arylxenon trifluoromethanesulfonates. Via this one-pot synthesis trifluoromethanesulfonates with the cations [Xe(2,4,6-F3C6H2)]+, [Xe(2-F-5-NO2C6H3)]+, [Xe(2-F-5-CF3C6H3)]+ and [Xe(3,5-(CF3)2C6H3)]+ were prepared. All compounds were characterized by their NMR, mass, and vibrational spectra.Additionally, several new arylxenon trifluoromethanesulfonates were detected by 129Xe-NMR spectroscopy as products of the reaction of 1,3-F2C6H4 and further deactivated benzenes with xenontrifluoroacetate trifluoromethane sulfonate.Fluoro substituents in ortho position to xenon significantly increase the thermal stability of the arylxenon trifluoromethanesulfonates obtained.The molecular structure of [Xe(2,6-F2C6H3)][OSO2CF3] was determined by single crystal diffraction methods. The arylxenon unit is weakly coordinated by one oxygen atom of the CF3SO3 anion. The salt crystallizes in the triclinic space group P1, a = 880.9(3) pm, b = 1093.9(5) pm, c = 1209.8(5) pm, α = 89.04(4)°, β = 74.23(3)°, γ = 86.03(3)°, Z = 4.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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