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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 602 (1991), S. 89-96 
    ISSN: 0044-2313
    Keywords: Pentafluorosulfanyl-substituted perfluorinated carbanions ; electrochemical and ESR investigation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electrochemical Investigations of SF5-Substituted CarbanionsThe perfluorinated carbanions SF5—C(CF3)2- and [(SF5)2C—CF3]- are sufficently stable in acetonitrile to be investigated by electrochemical methods. The oxidation of [(SF5)2C—CF3]- at +1.24 V (vs. SCE) results in the formation of the radical [(SF5)2C—CF3], which can be detected by ESR methods. The oxidation of [SF5—C(CF3)2]- at +1.55 V leads only to the radical (CF3)2C = C(CF3)2-, a secondary product. The carbanions [SF5—C(CF3)2]- and [(SF5)2C—CF3]-, the unsaturated compounds (SF5)2C = CF2, SF5—C(CF3) = CF2 and SF5—C(CH3) = CF2 as well as (SF5)2CH2 are irreversibly reduced at a potential range from -0.6 V to -0.8 V.
    Notes: Die perfluorierten Carbanionen [SF5—C(CF3)2]- und [(SF5)2C—CF3]- sind in Acetonitril hinreichend stabil, um elektrochemisch untersucht werden zu können. Die Oxidation von [(SF5)2C—CF3]- führt bei +1,24 V (vs. SCE) zu dem in ESR-Experiment beobachtbaren Radikal [(SF5)2C—CF3]. Für [SF5—C(CF3)2]-führt die Oxidation bei +1,55 V nur zu dem radikalischen Folgeprodukt (CF3)2C = C(CF3)2-. Die Carbanionen [SF5—C(CF3)2]- und [(SF5)2C—CF3]-, die ungesättigten Verbindungen (SF5)2C = CF2, SF5—C(CF3) = CF2 und SF5—C(CH3 = CF2) wie auch (SF5)2CH2 werden im Potentialbereich von -0,6 V bis -0,8 V irreversibel reduziert.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 557 (1988), S. 182-190 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal Structure of the SF5--AnionThe carbanion SF5—C(CF3)2- decomposes slowly forming SF5-, and (CF3)2C=C(CF3)2. The pentafluorosulfates(IV) grow in large crystals which are stable for prolonged times in presence of a SF4 vapour pressure. Crystal structure analysis of Rb+SF5- (Pbnm, a = 776.1(14), b = 990.3(5), c = 614.1(3) pm, Z = 4) revealed the SF5- anion in the expected square pyramidal structure. The axial bond is 15.9 pm shorter than the average equatorial bonds. The sulfur atom is located below the equatorial fluorine atoms. Pure Cs+SF5--crystals seem to be notoriously twinned. Accidentally we isolated a double salt (Cs+)6(SF5-)4 (HF2-)2 (P4b2, a = 1031.7(15), c = 627.6(9) pm, Z = 1). Herein the anion SF5- has the same structure as in Rb+SF5-.
    Notes: Das Carbanion SF5—C(CF3)2- zersetzt sich langsam zu SF5- und (CF3)2C=C(CF3)2. Die Pentafluorosulfate(IV) wachsen dabei in großen Kristallen, die in Gegenwart eines SF4-Gasdruckes längere Zeit haltbar sind. Die Kristallstrukturanalyse des Rb+SF5- (Pbnm, a = 776,1(14), b = 990,3(5), c = 614,1(3) pm, Z = 4) zeigt das SF5--Anion in seiner erwarteten quadratisch-pyramidalen Struktur. Die axiale Bindung ist beträchtliche 15,9 pm kürzer als die durchschnittliche äquatoriale S—F-Bindung. Auch befindet sich der Schwefel deutlich unterhalb der Ebene, die durch die vier äquatorialen Fluoratome gebildet wird.Vom reinen Cs+SF5- konnten bisher nur Zwillingskristalle erhalten werden. Durch Zufall gelang die Isolierung eines Doppelsalzes (Cs+)6(SF5-)4 (HF2-)2. Die Kristallstrukturanalyse (P4b2, a = 1031,7(15), c = 627,6(9) pm, Z = 1), zeigt das Vorhandensein der gleichen SF5-Struktureinheiten wie im Rb+SF5-.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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