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An angular overlap model treatment of mixed valence Pt(II)-Pt(IV) haloamine chain complexes

Behandlung von gemischt-wertigen Pt(II)-Pt(IV)-Ketten-Komplexverbindungen mit dem „Angular Overlap“-Modell

  • Anorganische Und Physikalische Chemie
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Summary

A recently proposed extension of the angular overlap model (AOM) is applied to the linear chain compounds [PtII(AA)2·PtIV X 2(AA)2] 4+∞ withX=Cl, Br, I;AA = ethylenediamine, 1,2- and 1,3-diaminopropane, and to Wolffram's red and Reihlen's green salt. The energy band structures are calculated from AOM parameters which are derived from d-d spectra of isolated Pt(II) and Pt(IV) complexes reported in the literature. Assignments of absorption edges and other peaks in the crystal spectra as well as spectral shifts due to changes in the geometric structure are discussed. Since the AOM energy expressions are given in analytical form, the procedure supplies various advantages over the extended Hückel theory which currently has been adapted for treating chain structures.

Zusammenfassung

Eine kürzlich vorgeschlagene Erweiterung des „Angular Overlap “-Modells (AOM) wird auf die linearen Kettenverbindungen [PtII(AA)2·PtIV X 2(AA)2] 4+∞ mitX=Cl, Br, I;AA = Ethylendiamin, 1,2- und 1,3-Diaminopropan sowie auf Wolfframs Rot-und Reihlens Grün-Salz angewandt. Die Energiebänder werden von AOM-Parametern berechnet, die aus d-d-Spektren isolierter Pt(II)- und Pt(IV)-Komplexe gewonnen wurden, welche in der Literatur zu finden sind. Diskutiert werden Zuordnungen zu Absorptionskanten und anderen Maxima in den Kristallspektren ebenso wie spektrale Verschiebungen aufgrund von Änderungen in der geometrischen Struktur. Da die AOM-Energieausdrücke in analytischer Form vorliegen, hat dieses Verfahren diverse Vorteile im Vergleich zur „Extended Hückel“-Theorie, die kürzlich ebenfalls so erweitert wurde, daß damit Kettenstrukturen behandelt werden können.

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Authors and Affiliations

  1. Institut für Theoretische Chemie, Universität Düsseldorf, D-4000, Düsseldorf 1, Federal Republic of Germany

    Hans-Herbert Schmidtke

  2. Institute of General and Inorganic Chemistry, Bulgarian Academy of Science, Sofia, Bulgaria

    Michael A. Atanasov

Authors
  1. Hans-Herbert Schmidtke
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  2. Michael A. Atanasov
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Schmidtke, HH., Atanasov, M.A. An angular overlap model treatment of mixed valence Pt(II)-Pt(IV) haloamine chain complexes. Monatsh Chem 120, 941–954 (1989). https://doi.org/10.1007/BF00808765

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  • DOI: https://doi.org/10.1007/BF00808765

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