Configurational stabilization of mixed-valence states in the star-burst tetranuclear ruthenium complex bridged with acetylene links
| Autor: | Jingyuan Chen, Hiroyasu Kamo, Koichi Aoki, Yoshimasa Hoshino |
|---|---|
| Rok vydání: | 1997 |
| Předmět: |
Valence (chemistry)
Chemistry General Chemical Engineering Inorganic chemistry chemistry.chemical_element Interaction energy Orbital overlap Electrochemistry Redox Analytical Chemistry Ruthenium Condensed Matter::Materials Science Crystallography chemistry.chemical_compound Acetylene Transition metal |
| Zdroj: | Journal of Electroanalytical Chemistry. 420:189-193 |
| ISSN: | 1572-6657 |
| Popis: | A new tetranuclear ruthenium complex in which a metal was bridged radially to three identical metals with acetylene links showed a mixed-valence state in cyclic voltammograms. The peak potential difference for the mixed-valence state was twice the potential difference for a mixed-valence state of the corresponding binuclear complex. This fact suggests stabilization of the mixed-valence state twice by configurational modification of redox centers. However, this is inconsistent with the prediction from the additive pair model of the redox interaction. A quantum chemical model of the redox interaction was presented, in which the potential difference was expressed by the overlap integral S and the nearest neighbor interaction energy between the reduced center and the oxidized one. Application of the theory gave a negative value of S, which demonstrated reasonably the stabilization of the mixed-valence state from a quantum chemical viewpoint. |
| Databáze: | OpenAIRE |
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