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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 106 (1973), S. 2845-2853 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aminyl Oxides, XIV. The Effect of Hetero Substituents at the Carbon Atom of Azomethine Aminyl Oxides on the Spin Distribution and the Geometry of the MoleculeAzomethine aminyl oxides substituted at the carbon atom of the azomethine group by hetero substituents X (5, 8) (type B) and radicals bridged by hetero substituents (4) (type A) were prepared. E.s.r. studies with A and B showed that the spin density is increased at the aminyl oxide nitrogen and decreased at the azomethine nitrogen by electron donating substituents. On the other hand electron accepting substituents favour delocalisation into the azomethine group. For radicals B additional steric effects become pronounced with increasing bulkiness of the group R1R2N.
    Notes: Azomethin-aminyloxide mit Heterosubstituenten X am C-Atom der Azomethingruppe (5, 8) (Typ B) und durch Heterosubstituenten verbrückte Radikale (4) (Typ A) wurden synthetisiert. Wie die ESR-spektroskopische Untersuchung ergab, verursachen Elektronendonator-Substituenten X in A und B eine Spindichteerhöhung am Aminyloxidstickstoff und eine Spindichteerniedrigung am Azomethinstickstoff. Durch Elektronenacceptor-Substituenten wird dagegen die Delokalisierung in die Azomethingruppe erhöht. In den Radikalen B werden mit wachsender Größe des Rests R1R2N zusätzlich sterische Effekte wirksam.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 106 (1973), S. 2832-2844 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aminyl Oxides, XIII. Relationship Between Spin Density Distribution and Geometry in Azomethine Aminyl OxidesVariously substituted azomethine aminyl oxides A and B (5, 24-30) were prepared and studied by e.s.r. spectroscopy. In radicals A the azomethine group and the aminyl oxide group were determined to be approximately coplanar for R = H, CH3, C2H5, whereas for R = CH(CH3)2 or more bulky groups these moieties were found to be twisted away from each other. With exception of 30 (R = CCl3) all radicals B studied by us were shown to have essentially coplanar azomethine and aminyl oxide groups. The azomethine aminyl oxides 33 having partially fixed geometry were synthesized for comparison.
    Notes: Verschiedenartig substituierte Azomethin-aminyloxide der Typen A und B (5, 24-30) wurden dargestellt und ESR-spektroskopisch untersucht. Dabei wurde für die Radikale A (R = H, CH3, C2H5) eine annähernd planare Anordnung der Azomethin- und Aminyloxid-gruppe gefunden, während mit sterisch anspruchsvolleren Resten (R = CH(CH3)2 und größer) eine starke Verdrillung dieser beiden Gruppen gegeneinander festgestellt wurde. Für die Radikale B läßt sich mit Ausnahme von 30 (R = CCl3) in allen anderen von uns untersuchten Fällen eine weitgehende Koplanarität von Azomethin- und Aminyloxidgruppe ableiten. Als Modellsubstanzen mit teilweise fixierter Molekülgeometrie wurden die Azomethin-aminyloxide 33 zum Vergleich herangezogen.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
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