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1995 Fiscal Year Final Research Report Summary

Activation of Small Inert Molecules

Research Project

Project/Area Number 04241104
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionUniversity of Tokyo

Principal Investigator

HIDAI Masanobu  U of Tokyo, Graduate School of Engineering, Professor, 大学院・工学系研究科, 教授 (60011011)

Co-Investigator(Kenkyū-buntansha) IWASAWA Yasuhiro  U of Tokyo, Graduate School of Science ; Professor, 大学院・理学系研究科, 教授 (40018015)
SAITO Taro  U of Tokyo, Graduate School of Science ; Professor, 大学院・理学系研究科, 教授 (90011006)
FUJIMOTO Kaoru  U of Tokyo, Graduate School of Engineering ; Professor, 大学院・工学系研究科, 教授 (30011026)
MURAI Shinji  Osaka U,Faculty of Engineering, Professor, 工学部, 教授 (00029050)
YOSHIDA Zen-ichi  Kinki U,Faculty of Science and Engineerig, Professor, 理工学部, 教授 (60025814)
Project Period (FY) 1992 – 1994
Keywordssmall inert molecule / dinitrogen / methane / carbon dioxide / metal cluster / solid surface
Research Abstract

The Objective of this research project lines in the establishment of chemical transformaitons using small inert molecules such as dinitrogen and methane which are abundant on earth, and carbon dioxide, the increase of which in the atmosphere arises from the use of fossil fuel by the human being and is becoming a serious environmental problems on a global scale. This is the fundamental and basic research towards the development of ideal chemical processes using carbon dioxide and methane as the simple carbon resourse and dinitrogen as the simple nitrogen resource to synthesize valuable organic compounds.
Efficient activation and chemical utilization of these small inert molecules are one of the most challenging subjects in chemistry. The main achievements in this project are described below.
1) The coordinated dinitrogen in molybdenum and tungsten phosphine complexes has been converted into nitrogen-heterocyclic compounds such as pyrrole and aminopyrrole via a series of reactions under mi … More ld conditions. Indole derivatives have also been synthesized from dinitrogen by using titanium systems. These results will open a new chemistry of nitrogen fixation where a variety of organo-nitrogen compounds are directly prepared from molecular nitrogen.
2) Electrochemical reduction of carbon dioxide on a copper electrode gives rise to the formation of methane, ethane, and ethanol. The reaction has been revealed to proceed through the formaiton of carbon monoxide as an intermediate on the electrode.
3) Selective electrochemical reduction of carbon dioxide to methanol has been for the first time realized by using redox enzymes as electrocatalysts.
4) Photoelectrochemical reduction of carbon dioxide on the p-type silicon electrode modified with ultrafine copper particles has led to the formation of methane and ethylene at a more positive potential than on a copper metal electrode.
5) New reactions have been developed which transform methane and carbon monoxide into acetic acids by using copper catalyst. This provides the first example of the carbon-carbon bond formation reactions of methane under mild conditions. Less

  • Research Products

    (10 results)

All Other

All Publications (10 results)

  • [Publications] H.Seino: "1-Pyrrolylimido Complexes of Molybdenum and Tungsten : Synthesis of Pyrrole from Molecular Dinitrogen and Unusual β-Regioselective Substitution Reactions of the Pyrrole Ring on a Metal Complex" J.Am.Chem.Soc.116. 7433-7434 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Chatani: "Ruthenium-Catalyzed Reaction of 1,6-Diynes with Hydrosilanes and Carbon Monoxide : A Third Way of Incorporating CO" J.Am.Chem.Soc.115. 11614-11615 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Fujimoto: "New Uses of Methane" Stud.Surf.Sci.Catal.81. 73-84 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Tsuge: "Synthesis of an Equilateral Triangular Molybdenum Cluster Complex [Mo_3(μ_3-S)(μ-S)_3(PMe_3)_6] with Eight Cluster Valence Electrons" J.Am.Chem.Soc.114. 7910-7912 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Ichikuni: "Observation of the Structural Change in the Nb Sites During Ethanol Dehydration on a SiO_2-Attached Nb Diner Catalyst by EXAFS" J.Phys.Chem.98. 11576-11581 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Seino et al.: "1-Pyrrolylimido Complexes of Molybdenum and Tungsten : Synthesis of Pyrrole from Molecular Dinitrogen and Unusual beta-Regioselective Substitution Reactions of the Pyrrole Ring on a Metal Complex" J.Am.Chem.Soc.116. 7433-7434 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N.Chatani et al.: "Ruthenium-Catalyzed Reaction of 1,6-Diynes with Hydrosilanes and Carbon Monoxide : A Third Way of Incorporating CO" J.Am.Chem.Soc.115. 11614-11615 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Fujimoto et al.: "New Uses of Methane" Stud.Surf.Sci.Catal.81. 73-84 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Tsuge et al.: "Synthesis of an Equilateral Triangular Molybdenum Cluster Complex [Mo_3 (mu_3-S) _2 (mu_2-) _3 (PMe_3) _6] with Eight Cluster Valence Electrons" J.Am.Chem.Soc.114. 7910-7912 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N.Ichikuni et al.: "Observation of the Structural Change in the Nb Sites During Ethanol Dehydration on a SiO_2-Attached Nb Diner Caralyst by EXAFS" J.Phys.Chem.98. 11576-11581 (1994)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1999-03-09  

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