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Electronic Communication in the Mixed-valence States of Cyclobutadienecobalt Complexes having Two Ferrocenes and Two Anthraquinones

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Abstract

Two geometric isomers, Z and E forms of (η4-cyclobutadiene)(η5-cyclopentadienyl) cobalt simultaneously containing two ferrocene moieties and two anthraquinone moieties, 1 and 2, respectively, were synthesized, and their crystal structures were determined. These molecules formed double mixed-valence states caused by ferrocene–ferrocenium and anthraquinone–anthrasemiquinone electronic communications. In both 1 and 2, the thermodynamic stability of the mixed-valence state for the ferrocene moieties was higher than that of the anthraquinone moieties because of the orbital coupling of the CB–Co bridging unit. The comproportionation constant, K c, for the ferrocene moieties was similar between 1 and 2, whereas the mixing coefficient, α, and the off-diagonal matrix-coupling element in the Marcus-Hush two-state model, H AB, evaluated from analysis of the intervalence charge transfer (IVCT) band were larger for 1 than for 2. These results suggest the existence of higher electrostatic repulsion between two ferrocenium cations in 1 than in 2 and the occurrence of through-bond electronic communication. K c for the anthraquinone moieties in the E form is smaller than that of the Z form, probably due to the through-space electronic interaction.

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Acknowledgments

This work was supported by Grants-in-Aid for Scientific Research (Nos. 16047204 (area 434) and 17205007), and CREST, Japan.

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Authors and Affiliations

  1. Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan

    Toshiyuki Nakaya, Kosuke Namiki, Masaki Murata, Katsuhiko Kanaizuka, Masashi Kurashina, Takako Fujita & Hiroshi Nishihara

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  1. Toshiyuki Nakaya
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  2. Kosuke Namiki
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  3. Masaki Murata
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  4. Katsuhiko Kanaizuka
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  5. Masashi Kurashina
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  6. Takako Fujita
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  7. Hiroshi Nishihara
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Correspondence to Hiroshi Nishihara.

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Nakaya, T., Namiki, K., Murata, M. et al. Electronic Communication in the Mixed-valence States of Cyclobutadienecobalt Complexes having Two Ferrocenes and Two Anthraquinones. J Inorg Organomet Polym 18, 124–130 (2008). https://doi.org/10.1007/s10904-007-9182-8

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