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  • 1
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations on the Mechanism of the Reductive Biphenyl Elimination from cis-Diphenylbis-(triphenylphosphane)platinum(II) Compounds: Influence of Electron Density at Platinum on Activation Parameters10 examples of the parent compound cis-bis(4-methoxyphenyl)bis(triphenylphosphane)platinum(II) modified by introduction of substituents of different character into the phenyl rings of the triphenylphosphane ligands have been synthesized. The activation parameters for the reductive elimination of 4,4′-dimethoxybiphenyl from these compounds have been determined. Despite the large distance between substituents and reaction center, a marked dependence on the electronic character of the substituents is observed. The free activation enthalpy is linearly correlated to the substituent constants and to the coupling constants 1J[195Pt,31P].
    Notes: 10 durch Einführung von Substituenten verschiedenen Charakters in die Phenyl-Ringe der Triphenylphosphan-Liganden modifizierte Vertreter der Stammverbindung cis-Bis(4-methoxyphenyl)-bis(triphenylphosphan)platin(II) wurden synthetisiert. An ihnen wurden die Aktivierungs-Parameter für die reduktive Eliminierung des 4,4′-Dimethoxybiphenyls bestimmt; sie demonstrieren  -  trotz der großen Entfernung der Substituenten vom Reaktionszentrum  -  eine ausgeprägte Abhängigkeit vom elektronischen Charakter der Substituenten. Die freie Aktivierungs-Enthalpie kann als lineare Funktion der Substituenten-Konstanten und der Kopplungskonstanten 1J[195Pt,31P] dargestellt werden.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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