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 journalArticlepeer-review

31 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

ASJC Scopus subject areas

  • Chemistry(all)

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