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Identification of the Reaction Products formed during a course of the Redox Process of a Coordinated Nitrosyl

Research Project

Project/Area Number 09640672
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionSophia University

Principal Investigator

MUKAIDA Masao  Sophia University, Faculty of Science and Engineering, Dept.of Chemistry, Professor, 理工学部, 教授 (00053596)

Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 1998: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1997: ¥2,700,000 (Direct Cost: ¥2,700,000)
KeywordsNitrosyl / Reduction product / mu_2-Nitrosyl complex / Nitrosyl-to-Nitro conversion / Ligand reaction / 電気化学
Research Abstract

The reaction between [Ru(NO)(H_2O)bpy_2]^<3+>({RuNO}^6) and formic acid gives [{Ru(mu-NO)}_2(bpy)_4]^<2+>, along with some other products species : cis-[Ru(NO)(OCHO)(bpy)_2]^<2+>([RuNO]^6) and cis-[Ru(OCHO)H_2O](bpy)_2]^+]. Structures of both complexes were confirmed by X-ray structure determination. The mu-nitrosyl complex consists of two cis-Ru(bpy)_2 fragments connected by two formally negatively charged bridging nitrosyl ligands. Electrochemical study of the complex shows that two successive one-electron oxidation wave to give[{Ru(mu-NO)}_2(bpy)_4]^<4+>({RuNO}^7-{RuNO}^7) are found. The generated two-electron oxidation species is disintegrated to afford a one-electron reduction species, cis-[Ru(NO^2)(CH_3CN)(bpy)_2]^<2+>({RuNO}^7), along with a small amount of an anexpected nitro species, cis-[Ru(NO_2)(CH_3CN)(bpy)_2]^+ this is the first observation which shows that the electrochemically induced nitrosyl-to-nitro conversion occurs in {RuNO}^7 type complex. The characteristics of electrochemicafly generated one-electron reduction species, cis-[Ru(NO^*)(x)(bpy)_2]^<(n-1)>, ({RuNO}^7) (x=H_2O,CH_3CN,ONO_2, NO_2, ONO, OCHO, OCOMe, Cl) were investigated in the connections. Among the complexes, X=ONO_2 complex gave easily cis-[Ru(NO_2)(CH_3CN)(bpy)_2^+. O ne possible explanation for the mechanistic process of the rare nitrosyl-to-nitro reaction was proposed.

Report

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

    (14 results)

All Other

All Publications (14 results)

  • [Publications] Hirotaka Nagao: "Synthesis and Electrochemical Behavior of the Complex having μ_2-Nitrosyl Moeity, as a Two-Electron Reduction Species of a {RuNO}^6-Type Nitrosyl, [{Ru(μ_2-NO)}_2(bpy)_4]^<2+>" Chemistry Letters. 473-474 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hirotaka Nagao: "Crystal Structure of Bis-(2, 2'-bipyridine)chloronitrosylruthenium(II)Perchlorate" Chemical Sciences. 14. 645-646 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hirotaka Nagao: "Evidence bfor a New Nitrosyl-to-Nitro Reaction and an Acetamide Formation in the{RuNO}^6-Type Complex, cis-[Ru(NO)(CH_3CN)(bpy)_2]^<3+>" Inorgahica Chimica Acta.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hirotaka Nagao: "Reductions of {RuNO}^6-Type Nitrosyl. Characteristics of the Two-Electron Reduction Species Isolated as the Complex Having a Fomally Negatively Charged μ-Nitrosyl Moiety and the One-Electron Reduction Species Generated Electrochemically" Bulletin of Chemical Society of Japan.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hirotaka Nagao, Dai Ooyama, F.Scott.Howell, Masao Mukaida, and Kunihiko Mizumachi: "Crystal Structure of Bis- (2,2'-bipyridine) -chloronitrosylruthenium (II) perchlorate" Analytical Science. Vol.14. 645-646 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hirotaka Nagao, Noriharu Nagao, Dai Ooyama, Yoshinobu Sato, Tooru Oosawa, Hiroshi Kuroda, F.Scott Howell, and Masao Mukaida.: "Synthesis and Electrochemical Behavior of the Complex Having mu-Nitrosyl Moiety, [{ Ru (mu-NO)} _2 (bpy) _4] ^<2+, , >" Chem.Lett.473-474 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hirotaka Nagao, Kyoko Ito, Naotoshi Tsuboya, Dai Ooyama, Noriharu Nagao, F.Scott Howell, and Masao Mukaida.: "Evidence for a New Nitrosyl-to-Nitro Reaction and an Acetamide Formation in the {RuNO} ^6-Type Complex, cis- [Ru (NO) (CH_3CN) (bpy) _2] ^<3+, , >" Inorg.Chim.Acta. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hirotak Nagao, Noriharu Nagao, Yasuhiko Yukawa, Dai Ooyama, Yoshinobu Sato, Tooru Oosawa, F.Scott Howell, and Masao Mukaida.: "Reductions of {RuNO} ^6-Type Nitrosyl. Characteristics of the Two-Electron Reduction Species Isolated as the Complex Having a Formally Negatively Charged mu-Nitrosyl Moiety ({ RuNO} ^8- {RuNO} ^8) and the One-Electron Reduction Species Generated Electrochemically ({RuNO} ^7)" Bull.Chem.Soc.Jpn.(Accepted).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hirotaka Nagao: "Synthesis and Electrochemical Behavior of the Complex having μ_2-Nitrosyl Moeity, as a Two-Electron Reduction Species of a {RuNO}^6-Type Nitrosyl, [{Ru (μ_2-NO)}_2 (bpy)_4] ^<2+>" Chemistry Letters. 473-474 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Hirotaka Nagao: "Crystal Structure of Bis- (2, 2'-bipyridine) chloronitrosylruthenium (II) Perchlorate" Chemical Sciences. 14. 645-646 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] D.Ooyama: "An Important Role of the One-Electron Reduction Nitrosyl Coordinated to Ruthenium." Bull.Chem.Soc.Jpn.70. 2141-2149 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] D.Ooyama: "One-Electron Oxidation Behavior of {MNO}^6-Type Nitrosyl Complexes having Acetylacetonato Ligand (M=Ru,Os)" Inorg.Chimica Acta. 261. 45-52 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Oomura: "Electrochemical Behavior of the Binuclear Ruthenium Complex having μ-Nitrosyl Ligand" Inorg.Chimica Acta. 269/2. 342-346 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Nagao: "Crystal Structure of Bis-(2,2'-bipyridine) chloronitrosylruthenium (II)" Analytical Science. 14 (in printing). (1998)

    • Related Report
      1997 Annual Research Report

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

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