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2006 Fiscal Year Final Research Report Summary

Structure Induction and Functioning of Metal Complexes Due to Weak Interactions

Research Project

Project/Area Number 16350036
Research Category

Grant-in-Aid for Scientific Research (B)

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

Principal Investigator

YAMAUCHI Osamu  Kansai University, Faculty of Engineering, Professor, 工学部, 教授 (70029643)

Co-Investigator(Kenkyū-buntansha) NAKABAYASHI Yasuo  Kansai University, Faculty of Engineering, Assoc.Professor, 工学部, 助教授 (70172385)
ODANI Akira  Nagoya University, Research Center for Materials Science, Assoc.Professor, 物質科学国際研究センター, 助教授 (60143913)
Project Period (FY) 2004 – 2006
KeywordsNoncovalent interactions / Aromatic amino acid / Aromatic ring stacking / Indole ring / Phenoxyl radical / Stability constant / Hydrogen bond / Bioinorganic Chemistry
Research Abstract

Amino acids are highly functional molecules with various side chain groups and essential components of proteins. Some of their functional groups are directly involved in enzyme activities, while others construct the microenvironment of the enzyme active center. We have been studying the weak interactions in metal complexes and revealed the presence of the hydrogen bonds and aromatic ring stacking interactions in metal complexes.
On the basis of the previous studies, we aimed at clarifying the structure determining ability of weak interactions, formation of molecular adducts, and their functions. In view of the biological significance of amino acids, we designed metal chelating agents incorporating the side chain groups of aromatic and aliphatic amino acids and synthesized their Cu(II), Pd(II), and Pt(II) complexes. Intramolecular aromatic ring stacking and other weak interactions in the complexes were investigated by various methods including stability constant determination and X-ray c … More rystal structure analysis. The studies revealed the following points : (1) the π-π stacking of the side chain aromatic ring with the metal-coordinated aromatic ring is stronger than that with an uncoordinated aromatic ring, and the large electron density difference between the interacting aromatic rings is favorable for the stacking ; (2) the binding of the indole ring with Pd(II) can occur at the N1 and the C3 atom in 3H-indole and gives rise to syn-anti isomers due to the binding at the tetrahedral C3 atom ; (3) the stability of the phenoxyl radical formed from metal-phenolate complexes by one-electron oxidation depends on both the central metal ion and the N-donor ability of the ligands ; (4) the methyl group from a branched alkyl side chain group often occupies the axial position with the C-metal distance of ca. 0.25 nm and shifts the redox potential of the Cu(II) center to a higher potential.
These results add to our understanding of the structure-function relationship in metal complexes and enzymes. Less

  • Research Products

    (17 results)

All 2007 2006 2005 2004 Other

All Journal Article (17 results)

  • [Journal Article] Syntheses and Electronic Structures of One-electron Oxidized Group 10 Metal(II)-(Disalicylidene)diamine Complexes (Metal = Ni, Pd, Pt)2007

    • Author(s)
      Yuichi Shimazaki, Tatsuo Yajima, Fumito Tani, Satoru Karasawa, Koichi Fukui, Yoshinori Naruta, Osamu Yamauchi
    • Journal Title

      J. Am. Chem. Soc. 129(9)

      Pages: 2559-2568

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis and Characterization of Imidazolate-Bridged Polynuclear Copper Complexes2007

    • Author(s)
      Takumi Higa, Masaki Moriya, Yuichi Shimazaki, Tatsuo Yajima, Fumito Tani, Satoru Karasawa, Motohiro Wakano, Yoshinori Naruta, Osamu Yamauchi
    • Journal Title

      Inorg. Chim. Acta (in press)

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] π-π Stacking Assisted Binding of Aromatic Amino Acids by Copper(II)-Aromatic Diimine Complexes. Effects of Ring Substituents on Ternary Complex Stability2007

    • Author(s)
      Tatsuo Yajima, Reiko Tamamido, Yuichi Shimazaki, Akira Odani, Yasuo Nakabayashi, Osamu Yamauchi
    • Journal Title

      Dalton Trans.

      Pages: 299-307

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Interactions o Flexible Diamine-bridged Dinuclear Ruthenium(II)-2,2'-Bipyridine Complexes with Mononucleotides and DNA2006

    • Author(s)
      Yasuo Nakabayashi, Nobuaki Iwamoto, Hiroyuki Inada, Osamu Yamauchi
    • Journal Title

      Chemistry Letters 2006(7)

      Pages: 722-723

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Indole Rings in Palladium(II) Complexes. Dual Mode of Metal Binding and Aromatic Ring Stacking Causing syn-anti Isomerism2006

    • Author(s)
      Masako Takani, Takeshi Takeda, Tatsuo Yajima, Osamu Yamauchi
    • Journal Title

      Inorganic Chemistry 45(15)

      Pages: 5938-5946

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] π-π Stacking Assisted Binding of Aromatic Amino Acids by Copper(II)-Aromatic Diimine Complexes. Effects of Ring Substituents on Ternary Complex Stability2006

    • Author(s)
      Tatsuo Yajima, Reiko Tamamido, Yuichi Shimazaki, Akira Odani, Yasuo Nakabayashi, Osamu Yamauchi
    • Journal Title

      Dalton Transactions 2007(2)

      Pages: 299-307

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Interactions of Flexible Diamine-bridged Dinuclear Ruthenium(II)-2,2'-Bipyridine Complexes with Mononucleotides and DNA2006

    • Author(s)
      Yasuo Nakabayashi, Nobuaki Iwamoto, Hiroyuki Inada, Osamu Yamauchi
    • Journal Title

      Chem.Lett.

      Pages: 722-723

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Iodine-Assisted Assembly of Helical Coordination Polymers of Cucurbituril and Asymmetric Copper(II) Complexes2005

    • Author(s)
      Feng Zhang, Tatsuo Yajima, Yi-Zhi Li, Guo-Zheng Xu, Hui-Lan Chen, Qi-Tao Liu, Osamu Yamauchi
    • Journal Title

      Angew. Chem. Int. Ed. 44(22)

      Pages: 3402-3407

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis and properties of triarylamine derivatives with coordination site and their complexes2005

    • Author(s)
      Masafumi Yano, Kazutoshi Inoue, Masaya Miyake, Takeshi Motoyama, Yasuhiro Azuma, Masakazu Tatsumi, Osamu Yamauchi, Munetaka Oyama, Kazunobu Sato, Takeji Takui
    • Journal Title

      Polyhedron 24

      Pages: 2112-2115

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Cyclopalladation of the Indole Ring in Palladium(II) Complexes of 2N1O-Donor Ligands and Its Dependence on the O-Donor Properties2005

    • Author(s)
      Yuichi Shimazaki, Minoru Tashiro, Takeshi Motoyama, Satoshi Iwatsuki, Tatsuo Yajima, Yasuo Nakabayashi, Yoshinori Naruta, Osamu Yamauchi
    • Journal Title

      Inorganic Chemistry 44(17)

      Pages: 6044-6051

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Iodine-Assisted Assembly of Helical Coordination Polymers of Cucurbituril and Asymmetric Copper(II) Complexes2005

    • Author(s)
      Feng Zhang, Tatsuo Yajima, Yi-Zhi Li, Guo-Zheng Xu, Hui-Lan Chen, Qi-Tao Liu, Osamu Yamauchi
    • Journal Title

      Angew.Chem.Int.Ed. 44(22)

      Pages: 3402-3407

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Cyclopalladation of the Indole Ring in Palladium(II) Complexes of 2N1O-Donor Ligands and Its Dependence on the O-Donor Properties2005

    • Author(s)
      Yuichi Shimazaki, Minoru Tashiro, Takeshi Motoyama, Satoshi Iwatsuki, Tatsuo Yajima, Yasuo Nakabayashi, Yoshinori Naruta, Osamu Yamauchi
    • Journal Title

      Inorg.Chem. 44(17)

      Pages: 6044-6051

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Nickel(II)-Phenoxyl Radical Complexes : Structure-Radical Stability Relationship2004

    • Author(s)
      Yuichi Shimazaki, Stefan Huth, Satoru Karasawa, Shun Hirota, Yoshinori Naruta, Osamu Yamauchi
    • Journal Title

      Inorganic Chemistry 43(24)

      Pages: 7816-7822

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Nickel(II)-Phenoxyl Radical Complexes : Structure-Radical Stability Relationship2004

    • Author(s)
      Yuichi Shimazaki, Stefan Huth, Satoru Karasawa, Shun Hirota, Yoshinori Naruta, Osamu Yamauchi
    • Journal Title

      Inorg.Chem. 43(24)

      Pages: 7816-7822

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Indole Rings in Palladium(II) Complexes. Dual Mode of Metal Binding and Aromatic Ring Stacking Causing syn-anti Isomerism

    • Author(s)
      Masako Takani, Takeshi Takeda, Tatsuo Yajima, Osamu Yamauchi
    • Journal Title

      Inorg.Chem. 45(15)

      Pages: 5938-5946

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Syntheses and Electronic Structures of One-electron Oxidized Group 10 Metal(II)-(Disalicylidene)diamine Complexes (Metal = Ni, Pd, Pt)

    • Author(s)
      Yuichi Shimazaki, Tatsuo Yajima, Fumito Tani, Satoru Karasawa, Koichi Fukui, Yoshinori Naruta, Osamu Yamauchi
    • Journal Title

      J.Am.Chem.Soc. 129(9)

      Pages: 2559-2568

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis and Characterization of Imidazolate-Bridged Polynuclear Copper Complexes

    • Author(s)
      Takumi Higa, Masaki Moriya, Yuichi Shimazaki, Tatsuo Yajima, Fumito Tani, Satoru Karasawa, Motohiro Wakano, Yoshinori Naruta, Osamu Yamauchi
    • Journal Title

      Inorg.Chim.Acta (in press)

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

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Published: 2008-05-27  

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