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Carbon Dioxide Fixation Accompanied by Carbon-carbon Bond Formation

Research Project

Project/Area Number 03453105
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionInstitute for Molecular Science

Principal Investigator

TANAKA Koji  Institute for Molecular Science (Professor), 分子科学研究所, 教授 (00029274)

Project Period (FY) 1991 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥6,800,000 (Direct Cost: ¥6,800,000)
Fiscal Year 1992: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1991: ¥5,500,000 (Direct Cost: ¥5,500,000)
KeywordsCarbon Dioxide / Multi-electron Reduction / eta^1-CO_2 Complex / Carbon-carbon Bond / Formation / 二酸化炭素固定 / αーケト酸 / η^1ーCO_2錯体 / CO_2の求核付加
Research Abstract

Photo- and electrochemical CO_2 reductions catalyzed by transition metal complexes have widely been investigated so far. The products in those homogeneous reactions, however, are limited to CO and/or HCOOH. The purpose of this project is to explore multi-electron reduction of CO_2 accompanied by carbon-carbon bond formation in electrochemical CO_2 reduction catalyzed by metal complexes. Isolation and the molecular structures by X-ray analysis for [Ru(bpy)_2(CO)_2]^<2+>, [Ru(bpy)_2(CO)(C(O)OH)]^+, and [Ru(bpy)_2(CO)(CO_2)] (bpy = 2,2'- bipyridyl) have revealed the mechanism for the formation of CO and HCOOH in the electro- and photochemical CO_2 reduction catalyzed by those complexes. Furthermore, the reaction of NaBH_4 with [Ru(bpy)_2(CO)_2]^<2+> at -20゚C to produce [Ru(bpy)_2(CO)(C(O)H)]^+, which is further reduced to [Ru(bpy)_2(CO)(CH_2OH)]^+ in the presence of excess of BH_<4-> at room temperature. From a point of view that both [Ru(bpy)_2(CO)(C(O)H)]^+ and [Ru(bpy)(trpy)(C(O)H)]^+ (trpy = terpyridyl) are quite labile at room temperature, electrochemical CO_2 reduction catalyzed by [Ru(bpy)(trpy)(CO)]^<2+> at -20゚C stabilizes the formyl intermediates, and CO_2 is catalytically reduced to not only HC(O)H and CH_3OH as the two- and four-electron reduction products but also HO(O)CC(O)H and HO(O)CCH_2OH as C2 products.Thus, [Ru(bpy)(trpy)(CO)]^<2+> has an ability to catalyze the multi-electron reduction accompanied by carbon-carbon bond formation in electrochemical CO_2 reduction.

Report

(3 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • Research Products

    (27 results)

All Other

All Publications (27 results)

  • [Publications] H.Tanaka: "Symthesis and Characterization of Bis(2,2^1-bipyridine)nitrocarbonylruthenium(II)Hexsafluorophoshate." Inorg.Chem.31. 1971-1973 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Tanaka: "Crystal Structure of cis-(Carbon monoxide)(η1-carbon dioxide)bis(2,2^1-bipyridine)ruthenium,an Active Species in Catalytic CO_2 Reduction Affording CO and HCOO^-." Organometallics. 11. 1450-1451 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Tanaka: "Structure and Bonding of cis-[Ru(bpy)_2(CO)(C(O)OCH_3)]B(C_6H_5)_4・CH_3CN(bpy=2,2^1-bipyridine)" Organometallics. 11. 3171-3172 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] N.Komeda: "Elrctrochemical Carbon Dioxide Fixation to Thioesters Catalyzed by [Mo_2Fe_6S_8(SEt)_9]^<3->." J.Am.Chem.Soc.114. 3625-3630 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Kambayashi: "(Ph_4As)_2[Fe_4S_4(SAd)_4and Stabilization of [Fe_4S_4(SAd)_4]^-Site in Aqueous Media." Chem.Lett.919-922 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Tanaka: "Comparative Study on Crystal Structures of [Ru(bpy)_2(CO)_2]PF_6,[Ru(bpy)_2(CO)(C(O)OCH_3)]B(C_6H_5)_4・CH_3CN,and[Ru(bpy)_2(CO)(η^1-CO_2)]・3H_2O(bpy=2,2^1-bipyridyl)" Inorg.Chem.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Tanaka: "Evaluation of Acidity of CO_2 in Protic Media.Carboxylation of Reduced Quinone." Chem.Lett.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Tanaka, H.Nagao, and K.Tanaka: "Synthesis and Characterization of Bis(2,2'-bipyridine)nitrocarbonylruthenium(II) Hexafluorophosphate" Inorg. Chem.31. 1971-1973 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Tanaka, H.Nagao, S-M.Peng, and K.Tanaka: "Crystal Structure of cis-(Carbon monoxide)(eta^1-carbon dioxide)bis(2,2'-bipyridine)ruthenium, an Active Species in Catalytic CO_2 Reduction Affording CO and HCOO^-" Organometallics. 11. 1450-14512 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Tanaka, B-C Tzeng, H.Nagao, and K.Tanaka: "Structure and Bonding of cis-[Ru(bpy)_2(CO)(C(O)OCH_3)]B(C_6H_5)_4・CH_3CN" Organometallics. 11. 3171-3172 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] N.Komeda, H.Nagao, T.Matsui, G.Adachi, and K.Tanaka: "Electrochemical Carbon Dioxide Fixation to Thioesters Catalyzed by [Mo_2Fe_6S_8(SEt)_9]^<3->" J. Am. Chem. Soc.114. 3625-3630 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Kambayashi, H.Nagao, S-M.Peng, and K.Tanaka: "Crystal Structure of (Ph_3As)_2[Fe_4S_4(SAd)_4] and [Fe_4S_4(SAd)_4]^- Site in Aqueous Media" Chem. Lett.919-922 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Tanaka, B-C Tzeng, H.Nagao, and K.Tanaka: "Comparative Study on Crystal Structures of [Ru(bpy)_2(CO)_2](PF_6)_2, [Ru(bpy)_2(CO)(C(O)OCH_3)] B(C_6H_5)_4・CH_3CN, and [Ru(bpy)_2(CO)(CO_2)]・3H_2O" Inorg. Chem.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Tanaka, H.Nagao, and K.Tanaka: "Evaluation of Acidity of CO_2 in Protic Media. Carboxylation of Reduced Quinone" Chem. Lett.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Tanaka: "Synthesis and Characterization of Bis (2,2'-bipyridine)nitrocarbonylruthenium(II)Hexsafluorophoshate." lnorg.Chem.31. 1971-1973 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Tanaka: "Crystal Structure of cis-(Carbon monoxide)(η1-carbon dioxide)bis(2,2'-bipyridine)ruthenium,an Active Species in Catalytic CO_2 Reduction Affording CO and HCOO^-." Organometallics. 11. 1450-1451 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Tanaka: "Structure and Bonding of cis-[Ru(bpy)_2(CO)(C(O)OCH_3)] B(C_6H_5)_4・CH_3CN(bpy=2,2'-bipyridine)" Organometallics. 11. 3171-3172 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] N.Komeda: "Electrochemical Carbon Dioxide Fixation to Thioesters Catalyzed by [Mo_2Fe_6S_8(SEt)_9]^<3->." J.Am.Chem.Soc.114. 3625-3630 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Kambayashi: "(Ph_4As)_2[Fe_4S_4(SAd)_4]and Stabilization of [Fe_4S_4(SAd)_4]^- Site in Aqueous Media." Chem.Lett.919-922 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Tanaka: "Comparative Study on Crystal Structures of[Ru(bpy)_2(CO)_2]PF_6,[Ru(bpy)_2(CO)(C(O)OCH_3)]B(C_6H_5)_4・CH_3CN,and[Ru(bpy)_2(CO)(η^1CO_2)]・3H_2O(bpy=2,2'-bipyridyl)" lnorg.Chem.

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Tanaka: "Evaluation of Acidity of CO_2 in Protic Media.Carboxylation of Reduced Quinone." Chem.Lett.

    • Related Report
      1992 Annual Research Report
  • [Publications] Nobutoshi Komeda: "Electrochemical Carbon Dioxide Fixation to Thioesters Catalyzed by [Mo_2Fe_6S_8(SPh)_9]^<3->." J.Am.Chem.Soc.

    • Related Report
      1991 Annual Research Report
  • [Publications] Koji Tanaka: "Electrochemical Assimilatory and Dissimilatory Reductions of NO^-_3 and NO^-_2 via a Possible Free NO Intermediate." Inorg.Chem.30. 3282-3288 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Koji Tanaka: "Redox Potential of Fe_4S_4 Cluster in Hydrophobic and Hydrophilic Spheres." Bull.Chem.Soc.Jpn.64. 1192-1197 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Hirotaka Nagao: "Carbon Dioxide Fixation Competed with Proton Addition to Methyl Acrylate." Chem.Lett.323-326 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Toshio Tanaka: "Chemical simulation of the nitrogen cycle and the carbon dioxide fixation in microbial systems." Trends in Inorganic Chemistry. 1. 41-49 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Hiroaki Tanaka: "Crystal Structure of cis-(Carbon monoxide)(η^1-Carbon dioxide) Bis(2,2^1-bipyridyl)ruthenium,an Active Species in Catalytic CO_2 Reduction Affording CO and HCOO^-." Organometallics.

    • Related Report
      1991 Annual Research Report

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Published: 1991-04-01   Modified: 2016-04-21  

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