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  • Inorganic Chemistry  (20)
  • Organic Chemistry  (11)
  • PHYSICS, SOLID-STATE  (7)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 332 (1964), S. 25-34 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The reaction enthalpy of silicon halides, SiX4 (X = Cl, Br, J) and also that of silicon with silver fluoride and hydrofluoric acid was measured. \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} {\rm SiX}_4 + 4{\rm AgF} + 2{\rm HF} = 4{\rm AgX} + {\rm H}_2 {\rm SiF}_6 \\{\rm Si}\quad + 4{\rm AgF} + 2{\rm HF} = 4{\rm Ag}\quad + {\rm H}_2 {\rm SiF}_6.\\\end{array} $$\end{document} The combination of these reaction enthalpies with the known ΔH°-values of the silver halides gives the enthalpies of formation of the silicon tetrahalides (at 298°K): \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l}\Delta{\rm H}^\circ ({\rm SiCl}_4,\,{\rm fl}) = - 163.9\,{\rm kcal}/{\rm Mol}\\\Delta{\rm H}^\circ ({\rm SiBr}_4,\,{\rm fl}) = - 108.4\,{\rm kcal}/{\rm Mol}\\\Delta{\rm H}^\circ ({\rm SiJ}_4,{\rm f})\quad = - 47.6\,{\rm Kcal}/{\rm Mol}.\\\end{array} $$\end{document} The results also confirm the lately measured high value for ΔH° (α-quartz).
    Notes: Die Reaktionsenthalpien der Siliciumhalogenide SiX4 (X = Cl, Br, J) sowie des Siliciums mit Silberfluorid und Flußsäure wurden gemessen. \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} {\rm SiX}_4 + 4{\rm AgF} + 2{\rm HF} = 4{\rm AgX} + {\rm H}_2 {\rm SiF}_6 \\{\rm Si}\quad + 4{\rm AgF} + 2{\rm HF} = 4{\rm Ag}\quad + {\rm H}_2 {\rm SiF}_6.\\\end{array} $$\end{document} Die Kombination dieser Reaktionsenthalpien mit den für die Silberhalogenide bekannten ΔH°-Werten liefert die Bildungsenthalpien der Siliciumtetrahalogenide (298°K): \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l}\Delta{\rm H}^\circ ({\rm SiCl}_4,\,{\rm fl}) = - 163,9\,{\rm kcal}/{\rm Mol}\\\Delta{\rm H}^\circ ({\rm SiBr}_4,\,{\rm fl}) = - 108,4\,{\rm kcal}/{\rm Mol}\\\Delta{\rm H}^\circ ({\rm SiJ}_4,{\rm f})\quad = - 47,6\,{\rm Kcal}/{\rm Mol}.\\\end{array} $$\end{document} Die Ergebnisse liefern ferner eine Bestätigung des neuerdings für α-Quarz gemessenen, hohen ΔH°-Wertes.
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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: Bis(trimethylsilyl)phosphates of 1,1,1,4,4,4-Hexafluoro-2,3-bis(trifluoromethyl)-2,3-butanediol and 1,1,1,3,3-Pentafluoro-2-propenolThe monocyclic phosphorane (EtO)3P[OC(CF3)2C(CF3)2O] 1 was hydrolized to give a mixture of an acyclic and a cyclic phosphate, 3 and 4.The trihydroxyphosphorane 2 could not be obtained. Iodotrimethylsilane 6 converts 1 into the silylated derivative of 4 which was found also besides (Me3SiO)2P(O)OC(CF3)2C(CF3)2OSiMe3 8 in the reaction of 3 and 4 with Me3SiCl/(Me3Si)2NH. (Me3SiO)3P 10 and hexafluoroacetone did not yield the tris(trimethylsiloxy)phosphorane 5, but the phosphonate 11 which gave (Me3SiO)2P(O)OC(CF3) — CF2 12 upon heating with the loss of fluorotrimethylsilane.
    Notes: Das monozyklische Phosphoran (EtO)3P[OC(CF3)2C(CF3)2O] 1 hydrolysierte zu einem Gemisch zweier Phosphorsäureester, einem azyklischen 3 und einem zyklischer 4, ohne daß das Trihydroxyphosphoran 2 erhalten werden konnte.Iodtrimethylsilan 6 überführte 1 in das silylierte Derivat von 4, welches neben (Me3SiO)2P(O)OC(CF3)2OSiMe3 8 auch bei der Umsetzung von 3 und 4 mit Me3SiCl/(Me3Si)2NH entstand. Die Reaktion von (Me3SiO)3P 10 mit Hexafluoraceton ergab kein Tris(trimethylsiloxy)-phosphoran 5, sondern den Phosphonsäureester 11, der beim Erhitzen unter Fluortrimethylsilanabspaltung in (Me3SiO)2P(O)OC(CF3) — CF2 12 überging.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 352 (1967), S. 258-264 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The enthalpies of formation of the solid halides NbBr5 and NbJ5 were measured in a solution calorimeter. As reference value we used δHº(NbCl5). Results: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} \Delta{\rm H}^0 ({\rm NbBr}_{\rm 5},\,298) = - 134.6\,(\pm \,1)\,{\rm Kcal}/{\rm mol} \\ \Delta{\rm H}^0 ({\rm NbJ}_5,\,298) = - 64.6\,(\pm 1)\,{\rm Kcal}/{\rm mol}. \\ \end{array} $$\end{document} Using the Born-Haber cycle and the structures of the pentahalides, values were derived for the enthalpy of formation of TaJ5, Δ Hº(TaJ5, 298) = -70 kcal/mol, and for the ionisation energy of Ta, J(Ta0→5) = 136 eV.
    Notes: Die Bildungsenthalpien für die festen Halogenide NbBr5 und NbJ5 wurden im Lösungs-kalorimeter bestimmt. Als Bezugsgröße diente δHº(NbCl5). Ergebnisse: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} \Delta{\rm H}^0 ({\rm NbBr}_{\rm 5},\,298) = - 134,6\,(\pm \,1)\,{\rm Kcal}/{\rm Mol} \\ \Delta{\rm H}^0 ({\rm NbJ}_5,\,298) = - 64,6\,(\pm 1)\,{\rm Kcal}/{\rm Mol}. \\ \end{array} $$\end{document} Unter Berücksichtigung des Born-Haberschen Kreisvorgangs und der Pentahalogenidstrukturen ergeben sich gute Näherungswerte für die Bildungsenthalpie von TaJ5, ΔHº(TaJ5, 298) = -70 kcal/Mol, und für die Ionisierungsspannung des Tantals J(Ta0→5) = 136 eV.
    Additional Material: 2 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 2986-2995 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Spirohexane Derivatives by Photosensitized Cycloadditions to MethylenecyclopropanePhotosensitized addition of maleic anhydride and some of its derivatives to methylenecyclopropane (1) gives spirohexanes in good yields. Dichlorovinylene carbonate and 1,3-diacetyl-4-imidazolin-2-one react with 1 in the same manner. In none of the reactions studied the formation of methylenecyclopentane derivatives was observed. A mechanism is suggested for the cycloadditions which involves as the initial step the terminal attack of the triplet excited components on the double bond of 1.
    Notes: Maleinsäureanhydrid und einige Derivate liefern bei der photosensibilisierten Addition an Methylencyclopropan (1) in guten Ausbeuten Spirohexane. Entsprechend reagieren auch Dichlorvinylencarbonat und 1,3-Diacetyl-4-imidazolin-2-on mit 1. In keiner der untersuchten Reaktionen gibt es Hinweise auf die Bildung von Methylencyclopentan-Derivaten. Als Mechanismus für die Cycloadditionen wird ein primärer terminaler Angriff der triplettangeregten Komponenten an die Doppelbindung von 1 formuliert.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 113 (1980), S. 1884-1889 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Diastereomeric 2-AminocyclobutanolsSyntheses of the previously unknown 2-aminocyclobutanols are described. The cis-isomer (5) is obtained in two steps by photosensitized cycloaddition of 4-oxazolin-2-one (1) or its acetyl derivative 2 to ethylene and subsequent alkaline hydrolysis of the adducts. Synthesis of the trans-isomer (6) is achieved by catalytic hydrogenation of trans-2-azidocyclobutanol (19), which is available in two steps from the cyclic orthobenzoate 12 and -acetate 13, resp., of cis-1,2-cyclobutanediol (11).
    Notes: Synthesen der diastereomeren 2-Aminocyclobutanole werden erstmals beschrieben. Das cis-Isomere (5) erhält man in zwei Stufen durch photosensibilisierte Cycloaddition von 4-Oxazolin-2-on (1) bzw. dessen Acetyl-Derivat 2 an Ethylen und folgende alkalische Hydrolyse der Addukte. Das trans-Isomere (6) ist durch katalytische Hydrierung des trans-2-Azidocyclobutanols (19) zugänglich, das man in zwei Stufen aus dem cyclischen Orthobenzoat 12 bzw. -acetat 13 des cis-1,2-Cyclobutandiols (11) gewinnt.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 9 (1836), S. 204-209 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 10 (1837), S. 65-78 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 8
    ISSN: 0009-2940
    Keywords: Bulky substituents ; Aluminum compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Structure of CpAlCl2 Compounds with Sterically Demanding Substituents (Cp = Me5C5, EtMe4C5)[1]The compounds Cp*AlCl2 (3) (Cp* = Me5C5) and Cp′AlCl2 (4) (Cp′ = EtMe4C5) have been prepared by the reaction of Cp*SiMe3 (1) and Cp′SiMe3 (2) with AlCl3. The single-crystal X-ray structures of 3 and 4 are reported.
    Additional Material: 2 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1445-1446 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ethylidenephosphorane - Ethenylfluorophosphorane (2λ5σ4P-λ5σ5P) Rearrangement2-Methoxy-1,3,2-dioxaphospholane (4) reacts with 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithietane (1) to furnish 2-methoxy-2-[2,2,2,-trifluoro-1-(trifluoromethyl)ethylidene]-1,3,2λ 5σ5-dioxaphospholane (6) which rearranges upon standing at ambient temperature to form 2-[2,2-difluoro-1-(trifluoromethyl)ethenyl]-2-fluoro-2-methoxy-1,3,2λ5σ5-dioxaphospholane (7).
    Notes: No Abstract
    Additional Material: 1 Tab.
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  • 10
    ISSN: 0009-2940
    Keywords: Sulfur diimides ; 1,3-Cycloaddition, reductive ; 1,2,4,3-Thiadiazaboretidines ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Properties of 1,2,4,3-Thiadiazaboretidines. Crystal Structure of 2,4-Di-tert-butyl-3-phenyl-1,2,4,3-thiadiazaboretidineReaction of sulfur diimides with alkyl(aryl)bis(methylthio)boranes leads to reductive 1,3-cycloaddition of the NSN sequence with formation of the 1,2,4,3-thiadiazaboretidines 2a-g. NMR (1H, 11B, 13C, 15N, 29Si), mass spectra and the results of the X-ray analysis of 21 are reported and discussed. The 11B chemical shifts have been calculated for 3-phenyl-1,2,4,3-thiadiazaboretidine and some related model compounds by the IGLO method and correlate acceptably with the experimental values.
    Additional Material: 1 Ill.
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