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Valence Fluctionality of Trinuclear Ruthenium Complex Dimers

Research Project

Project/Area Number 09044054
Research Category

Grant-in-Aid for international Scientific Research

Allocation TypeSingle-year Grants
SectionJoint Research
Research Field Inorganic chemistry
Research InstitutionTohoku University

Principal Investigator

ITO Tasuku  Tohoku University, Graduate School of Science Department of Chemistry, Professor, 大学院・理学研究科, 教授 (90007328)

Co-Investigator(Kenkyū-buntansha) KUBIAK Cliff  カリフォルニア大学サンディエゴ校, 教授
YAMAGUCHI Tadashi  Tohoku University, Graduate School of Science Department of Chemistry, Research, 大学院・理学研究科, 助手 (40230362)
KUBIAK Clifford P.  Purdue University, Department of Chemistry, Professor
Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥4,900,000 (Direct Cost: ¥4,900,000)
Fiscal Year 1998: ¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1997: ¥2,600,000 (Direct Cost: ¥2,600,000)
KeywordsMixed Valence State / Spectroelectrochemistry / Intramolecular Electron Transfer / Coalescence / Charge Transfer Complex / Conproportionation Constant / Intervalence Band / Rutheniumu Cluster
Research Abstract

lntramolecular electron transfers within the mixed valence states of the ligand bridged hexaruthenium clusters Ru_3(mu_3-O)(mu-CH_3CO_2)_6(CO)(L)(mu-L')Ru_3(mu_3-O)(mu-CH_3CO_2)_6(CO)(L)(L' = 1,4-pyrazine ; L = 4-dimethyl-aminopyridine (1), pyridine (2), 4-cyanopyridine (3), or L' = 4,4'-bipyridine ; L = 4-dimethyl-aminopyridine (4), pyridine (5), 4-cyanopyridine (6) were examined. Two discrete and reversible single electron reductions are evident by cyclic voltammetry in the redox chemistry of 1 - 5, and the inter-cluster charge transfer complexes are well defined. The splitting of the reduction waves, E, is related to the electronic coupling H_<AB> between the triruthenium clusters, and varies from 80 mV for 5 to 440 mV for 1. In the case of 6, the splitting of the reduction waves, E, is < 50 mV and the inter-cluster charge transfer complex is not defined. The mixed valence states of 1 - 3 also exhibit intervalence charge transfer (ICT) bands in the region 12,100 cm^<-1> (1) to 10,80 … More 0 cm^<-1> (3) which provide spectroscopic estimates of H_<AB> in the range 2180 cm^<-1> (1) to 1310 cm^<-1> (3). The magnitude of the electronic coupling H_<AB> is found to strongly influence the IR spectra of the singly reduced (-1) mixed valence states of 1 - 6 in the n(CO) region. In the case of relatively weak electronic coupling (4 - 6), two v(CO) bands are clearly resolved. In the cases of strong electronic coupling (1 - 3), these bands broaden to a single v(CO) absorption band. These data allow the rate constants, kappa_c, for electron transfer in the mixed valence states of 1, 2, and 3 to be estimated by simulating dynamical effects (Bloch type equations) on v(CO) absorption bandshape at 9 x 10^<11> s^<-1>, 5 x l0^<11> s^<-1>, and ca . 1 x 10^<11> s^<-1>, respectively. The less strongly coupled 4,4'-bipyridine bridged complexes 4 - 6 exhibit IR lineshapes in the -1 mixed valence states that are not as strongly affected by electron transfer dynamics. The rate constant for the -1 mixed valence state of 4 is close to the lower limit that can be estimated by this approach, between 1 x 10^<10> and 1 x 10^<11> s^<-1>. Less

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • Research Products

    (10 results)

All Other

All Publications (10 results)

  • [Publications] 伊藤 翼: "Effects of Rapid Intramolecular Electron Transfer on Vibrationl Spectra." Science. 277. 660-663 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 伊藤 翼: "Electron Transfer on the Infrared Vibrational Time Scale in the Mixed Valence State of 1, 4-Pyrazine and 4,4′-Bipyridine Bridged Ruthenium Cluster Complexes." Journal of the American Chemical Society. 発表予定.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 伊藤 翼: "Syntheses and Properties of a Series of Oxo-Centered Triruthenium Complexes and Their Bridged Dimers with Isocyanide Ligands at Terminal and Bridging Positions." Inorganic Chemistry. 発表予定.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Tasuku Ito, Tomohiko Hamaguchi, Haruko Nagino, Tadashi Yamaguchi, John Washington, and Clifford Kubiak: "Effects of Rapid Intramolecular Electron Transfer on Vibrational Spectra" Science. 277. 660-663 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Tasuku Ito, Tomohiko Hamaguchi, Haruko Nagino, Tadashi Yamaguchi, Hiroaki Kido, Igor S.Zavarine, Todd Richmond, John Washington, and Clifford P.Kubiak: "Electron Transfer on the Infrared Vibrational Time Scale in the Mixed Valence State of 1,4-Pyrazine and 4,4'-Bipyridine Bridged Ruthenium Cluster Complexes" J.Am.Chem.Soc.(submitted for publication).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Ken-ichiro Ota, Hirokazu Sasaki, Taeko Matsui, Tomohiko Hamaguchi, Tadashi Yamaguchi, Tasuku Ito, Hiroaki Kido, and Clifford P.Kubiak: "Syntheses and Properties of a Series of Oxo-Centered Triruthenium Complexes and Their Bridged Dimers with Isocyanide Ligands at Terminal and Bridging Positions" Inorg.Chem.(submitted for publication).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 伊藤 翼: "Effects of Rapid Intramolecular Electron Transfer on Vibrationl Spectra." Science. 277. 660-663 (1997)

    • Related Report
      1998 Annual Research Report
  • [Publications] 伊藤 翼: "Electron Transfer on the Infrared Vibrational Time Scale in the Mixed Valence State of 1,4-Pyrazine and 4,4'-Bipyridine Bidged Ruthenium Cluster Complexes." Journal of the American Chemical Society. (発表予定).

    • Related Report
      1998 Annual Research Report
  • [Publications] 伊藤 翼: "Syntheses and Properties of a Series of Oxo-Centered Triruthenium Complexes and Their Bridged Dimers with Isocyanide Ligands at Terminal and Bridging Positions." Inorganic Chemistry. (発表予定).

    • Related Report
      1998 Annual Research Report
  • [Publications] 伊藤 翼: "Effects of Rapid Intramolecular Electron Transfer on Vibrationl Spectra" Science. 277. 660-663 (1997)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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