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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1976 (1976), S. 300-316 
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Coordination Compounds of the Type C5H5Cr(CO)(NO)L Containing Olefin and Acetylene LigandsThe photoinduced substitution of a CO ligand in C5H5Cr(CO)2(NO) (1) has been used to prepare olefin and acetylene x-complexes of the type C5H5Cr(CO)(NO)L 2, which possess a center of chirality at the metal. In addition to C5H5Cr(CO)(NO)L compounds with L = ethylene: 2a, propene: 2b or styrene: 2c, two groups of olefin complexes have been investigated: complexes containing cycloolefins 2d-m, and complexes containing acceptor olefins 2n-t of the maleic and fumaric acid type. For purposes of comparison, some C5H5Cr(CO)(NO)L compounds 2u-z with L = alkyne have also been isolated. The complexes have been characterised by typical IR- and 1H-N MR spectroscopic data; in some cases, hindered rotation of the x-bonded ligand L has been deduced from the temperature dependence of the 1H-NMR spectra. The complex of 1,5-cyclooctadiene, C5H5Cr(CO)(NO)C8H12 (21), is easily converted into the binuclear derivative C8H12[C5H5Cr(CO)(NO)]2 (3l) containing a bridging 1,5-cyclooctadiene ligand.
    Notes: Durch photoinduzierte Substitution eines CO-Liganden in C5H5Cr(CO)2NO (1) wurden Olefin- und Acetylen-n-Komplexe des Typs C5H5Cr(CO)(NO)L, 2 dargestellt, die am Zentralmetall ein Chiralitatszentrum besitzen. Neben den CH5Cr(CO)(NO)L-Verbindungen mit L = Äthylen: 2a, Propen: 2b und Styrol: 2c wurden zwei Gruppen von Olefinkomplexen untersucht: Zum einen Komplexe mit Cycloolefinen 2d-m, zum anderen Komplexe mit Akzeptorolefinen 2n-t der Malein- oder Fumarsäurereihe; zum Vergleich wurden einige CsHsCr(CO)(NO)L-Verbindungen 2u-z mit L = Alkin dargestellt. Die Komplexe wurden anhand typischer IR- und 1H-NMR-Daten charakterisiert; in einigen Fällen konnte anhand der temperaturabhängigen 1H-NMR-Spektren auf eine gehinderte Rotation des x-gebundenen Liganden L geschlossen werden. Der Komplex des 1,5-Cyclooctadiens, C5H5Cr(CO)(NO)CgH12 (21), wandelt sich leicht in das zweikernige Derivat C8H12[C5H5Cr(CO)(NO)]2 (3l) um, das eine 1,5-Cyclooctadien-Brücke enthalt.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1976 (1976), S. 292-299 
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photoinduced Preparation of Complexes of the Type C5H5Cr(CO)(NO)LPhotolysis of C5H5Cr(C0)2NO (3) in solution can be used to prepare rnonosubstituted complexes C5H5Cr(CO)(NO)L 4, if the solvent itself behaves as a coordinating ligand L and possesses acceptor properties (e. g., L = acetonitrile, pyridine or cycloolefin). A more versatile method for the preparation of complexes C5H5Cr(CO)(NO)L is based on the fact that the ligand cyclooctene in C5H5Cr(CO)(NO)C8H14 (prepared photolytically) is displaced by many gaseous, liquid and solid two-electron ligands L. As an example, the preparation and characterisation are described of some complexes 4 with N-containing ligands (L = acetonitrile: 4a, pyridine: 4b, y-picoline: 4c and 2,3-diazabicyclo[2.2.l]hept-2-ene: 4d). In THF photolysis of 3 results in elimination of both CO ligands.
    Notes: Die Photolyse von C5H5Cr(CO)zNO (3) in Lösung läßt sich zur Darstellung monosubstituierter Komplexe C5H5Cr(CO)(NO)L, 4 anwenden, wenn das Solvens selbst als Koordinationsligand L fungieren kann und Akzeptoreigenschaften besitzt (z. B. L = Acetonitril, Pyridin oder Cycloolefin). Eine vielseitigere Methode zur Gewinnung von Komplexen C5H5Cr(CO)(KO)L macht von der Tatsache Gebrauch, daß der Ligand Cycloocten in dem photolytisch zugänglichen Komplex C5H5Cr(CO)(NO)C8H14 durch zahlreiche gasförmige, flüssige oder feste Zweielektronenliganden L ersetzt werden kann. Als Beispiel wird über Darstellung und Charakterisierung einiger Komplexe 4 mit N-haltigen Liganden berichtet (L = Acetonitril: 4a, Pyridin: 4b, γ-Picolin: 4c, 2,3-Diazabicyclo[2.2.l]hept-2-en: 4d). In THF verläuft die Photolyse von 3 unter Abspaltung beider CO-Liganden.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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