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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 3896-3908 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Complexes of N-Containing Ligands, II. Coordination Compounds of the Type C5H5Mn(CO)2L Involving Organic NitrilesOrganic nitriles R—C≡N (L) add to the complex fragment [C5H5Mn(CO)2], generated by photolysis in THF solution, with the lone pair of electrons on the nitrogen atom of the cyano group. A series of C5H5Mn(CO)2L complexes 3 containing either aliphatic (acetonitrile, phenylacetonitrile), α-β-unsaturated (fumarodinitrile, cinnamonitrile) or aromatic nitriles (benzonitrile, pentafluorobenzonitrile, p-substituted benzonitriles) have been prepared and characterized on the basis of their infrared, 1H-n. m. r. and electronic spectra. Strong interaction is observed between the free and the metal-coordinated cyano groups in the C5H5Mn(CO)2L complexes of fumarodinitrile (3a) and terephthalonitrile (3f).
    Notes: Organische Nitrile R—C≡N (L) der aliphatischen (Acetonitril, Phenylacetonitril), der olefinischen (Fumarsäuredinitril, Zimtsäurenitril) und der aromatischen Reihe (Benzonitril, Pentafluorbenzonitril, p-substituierte Benzonitrile) lagern sich über das freie Elektronenpaar am Stickstoffatom der Cyangruppe an das in THF-Lösung photolytisch erzeugte Komplexfragment [C5H5Mn(CO)2] an. Die entstehenden Nitril-Komplexe 3 werden anhand ihrer IR-, 1H-NMR- und Elektronenspektren charakterisiert. In den C5H5Mn(CO)2L-Verbindungen des Fumarsäuredinitrils (3a) und des Terephthalsäuredinitrils (3f) läßt sich eine starke Wechselwirkung zwischen der freien und der koordinativ gebundenen Cyangruppe beobachten.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 3909-3917 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Complexes of N-Containing Ligands, III. Donor-Acceptor Properties of Organic Nitriles in the C5H5Mn(CO)2L SystemThe ligand properties of organic nitriles (L) in complexes of the general type C5H5Mn(CO)2L are discussed on the basis of the following four spectroscopic parameters: a) the difference ΔνC≡N between the C≡N stretching frequencies of the free and the metal-coordinated nitrile, b) the valence force constant k(C≡O) of the two carbonyl groups, c) the chemical shift τC5H5 of the cyclopentadienyl ring protons in acetone-d6, and d) the energy of the maximum of the manganese-to-nitrile charge transfer band \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde{\nu} $\end{document}max(CT). A linear relationship is found to exist between these four parameters and the Hammett constants σp of the substituents Z in p-substituted benzonitrile complexes, C5H5Mn(CO)2(NC—C6H4—Z).
    Notes: Für die Diskussion der Liganden-Eigenschaften organischer Nitrile (L) in Komplexen des Typs C5H5Mn(CO)2L werden vier spektroskopische Parameter herangezogen: a) die Frequenzdifferenz ΔνC≡N zwischen der Nitril-Streckschwingung des freien und des koordinativ gebundenen Nitrils, b) die Valenzkraftkonstante K(C≡O) der beiden Carbonyl-Gruppen, c) die chemische Verschiebung τC5H5 der Cyclopentadienyl-Ringprotonen in Aceton-d6 und d) die Energie des Absorptionsmaximums der Mangan→Nitril-CT-Bande \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde{\nu} $\end{document}max(CT). In den Verbindungen C5H5Mn(CO)2(NC—C6H4—Z) mit p-substituierten Benzonitrilen besteht eine lineare Beziehung zwischen diesen vier Parametern und den Hammett-Konstanten σ p der Ringsubstituenten Z.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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