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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: Synthese and Spectroscopic Investigations of Substituted cis- and trans-Dichlorobis-(triphenylphosphane)platinum(II) CompoundsCompounds of the type cis- and trans-dichlorobis(triphenylphosphane)platinum(II) (3) with substituents of different electronic character in the phenyl rings bonded to phosphorus have been synthesized. The coupling constants 1J[195Pt,31P] and the chloro-platinum valence vibrational frequencies are demonstrated to be criteria for unambiguous discrimination between cis- and trans-configurations at platinum; a linear correlation exists between the sum of the ρ-constants of the substituents at the triphenylphosphane and the coupling constants 1J[195Pt,31P].
    Notes: Verbindungen des Typs cis- und trans-Dichlorobis(triphenylphosphan)platin(II) (3), deren an den Phosphor gebunden Phenyl-Ringe in verschiedenen Positionen mit Substitutenten unterschiedlichen elektronischen Charakters substituiert sind, werden dargestellt. Mit den Kopplungskonstanten 1J[195Pt, 31P] und den Platin-Chlor-;Valenzschwingungsfrequenzen werden Kriterien für die sichere Unterscheidung zwischen cis- und trans-Konfiguration am Platin aufgezeigt; es besteht ein linearer Zusammenhang zwischen der Summe der Substituenten-Konstanten der in das Triphenylphosphan eingeführten Substituenten und den Kopplungskonstanten 1J[195Pt, 31P].
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    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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