14 Step-15 electron reversible redox behavior of tetrameric oligomer of oxo-bridged triruthenium cluster

Tomohiko Hamaguchi, Haruko Nagino, Katsunori Hoki, Hiroaki Kido, Tadashi Yamaguchi, Brian K. Breedlove, Tasuku Ito

    Research output: Contribution to journalArticle

    30 Citations (Scopus)

    Abstract

    Pyrazine-bridged trimeric and tetrameric oligomers of triruthenium clusters, [{Ru 3O(CH 3CO 2) 6(CO)(Py)}- (μ-pz)-{Ru 3O(CH 3CO 2) 6(CO)}-(μ- pz)-{Ru 3O(CH 3CO 2) 6(py) 2}] + (1), and [{Ru 3O(CH 3CO 2) 6(CO)(py)}-(μ-pz)-{Ru 3O-(CH 3CO 2) 6(CO)}-(μ-pz)-{Ru 3O(CH 3CO 2) 6(py)}-(μ-pz)-{Ru 3O(CH 3CO 2) 6(dmap) 2}] 2+ (2), were prepared (pz = pyrazine, py = pyridine, dmap = 4-dimethylaminopyridine). Trimer 1 and tetramer 2 show closely spaced 11 step-12 electron and 14 step-15 electron reversible redox waves, respectively, in their cyclic voltammograms in CH 3CN. These compounds were designed specifically to incorporate the above-mentioned electrochemical behavior, using the unique redox properties characteristic of triruthenium clusters: (i) each Ru 3 cluster unit generally exhibits four reversible single electron waves from Ru 3 IV,III,III to Ru 3 II,II,II state; (ii) the redox potentials of the cluster units strongly depend on the basicity of the ancillary ligand; (iii) redox potentials of the Ru 3 cluster units vary by 300-500 mV depending on the presence or the absence of a carbonyl ligand on the cluster unit; (iv) in the negative potential region, electronic interaction through the bridging pyrazine between adjacent Ru 3 units containing a carbonyl ligand makes the difference in redox potential of each unit larger. 1 and 2 were synthesized by linking Ru 3 cluster units with the desired ancillary ligand set in the appropriate order.

    Original languageEnglish
    Pages (from-to)591-598
    Number of pages8
    JournalBulletin of the Chemical Society of Japan
    Volume78
    Issue number4
    DOIs
    Publication statusPublished - 2005 Apr 15

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    Oligomers
    Carbon Monoxide
    Pyrazines
    Electrons
    Ligands
    Alkalinity
    Oxidation-Reduction

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    14 Step-15 electron reversible redox behavior of tetrameric oligomer of oxo-bridged triruthenium cluster. / Hamaguchi, Tomohiko; Nagino, Haruko; Hoki, Katsunori; Kido, Hiroaki; Yamaguchi, Tadashi; Breedlove, Brian K.; Ito, Tasuku.

    In: Bulletin of the Chemical Society of Japan, Vol. 78, No. 4, 15.04.2005, p. 591-598.

    Research output: Contribution to journalArticle

    Hamaguchi, Tomohiko ; Nagino, Haruko ; Hoki, Katsunori ; Kido, Hiroaki ; Yamaguchi, Tadashi ; Breedlove, Brian K. ; Ito, Tasuku. / 14 Step-15 electron reversible redox behavior of tetrameric oligomer of oxo-bridged triruthenium cluster. In: Bulletin of the Chemical Society of Japan. 2005 ; Vol. 78, No. 4. pp. 591-598.
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    abstract = "Pyrazine-bridged trimeric and tetrameric oligomers of triruthenium clusters, [{Ru 3O(CH 3CO 2) 6(CO)(Py)}- (μ-pz)-{Ru 3O(CH 3CO 2) 6(CO)}-(μ- pz)-{Ru 3O(CH 3CO 2) 6(py) 2}] + (1), and [{Ru 3O(CH 3CO 2) 6(CO)(py)}-(μ-pz)-{Ru 3O-(CH 3CO 2) 6(CO)}-(μ-pz)-{Ru 3O(CH 3CO 2) 6(py)}-(μ-pz)-{Ru 3O(CH 3CO 2) 6(dmap) 2}] 2+ (2), were prepared (pz = pyrazine, py = pyridine, dmap = 4-dimethylaminopyridine). Trimer 1 and tetramer 2 show closely spaced 11 step-12 electron and 14 step-15 electron reversible redox waves, respectively, in their cyclic voltammograms in CH 3CN. These compounds were designed specifically to incorporate the above-mentioned electrochemical behavior, using the unique redox properties characteristic of triruthenium clusters: (i) each Ru 3 cluster unit generally exhibits four reversible single electron waves from Ru 3 IV,III,III to Ru 3 II,II,II state; (ii) the redox potentials of the cluster units strongly depend on the basicity of the ancillary ligand; (iii) redox potentials of the Ru 3 cluster units vary by 300-500 mV depending on the presence or the absence of a carbonyl ligand on the cluster unit; (iv) in the negative potential region, electronic interaction through the bridging pyrazine between adjacent Ru 3 units containing a carbonyl ligand makes the difference in redox potential of each unit larger. 1 and 2 were synthesized by linking Ru 3 cluster units with the desired ancillary ligand set in the appropriate order.",
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    AU - Kido, Hiroaki

    AU - Yamaguchi, Tadashi

    AU - Breedlove, Brian K.

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