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1998 Fiscal Year Final Research Report Summary

Model Complexes for Non-Redox Active Metalloenzymes(Structural and Functional Model Complexes for Non-Redox Active Metalloenzymes Involving Dinuclear Metal Centers)

Research Project

Project/Area Number 09044103
Research Category

Grant-in-Aid for international Scientific Research

Allocation TypeSingle-year Grants
SectionJoint Research .
Research Field Inorganic chemistry
Research InstitutionNara Women's University

Principal Investigator

TANASE Tomoaki  Nara Women's University, Faculty of Science, Associate Professor, 理学部, 助教授 (50207156)

Co-Investigator(Kenkyū-buntansha) LIPPARD J.Stephen  Massachusetts Institute of Technology, Department of Chemistry, Professor, 化学科, 教授
YANO Shigenobu  Nara Women's University, Faculty of Science, Professor, 理学部, 教授 (60011186)
Project Period (FY) 1997 – 1998
Keywordsmetalloenzymes / dimetal centers / biomimetic models / carboxylate bridges / carbohydrates / phosphate esters / hydrolysis / isomerization
Research Abstract

1. Carboxylate-bridged dinuclear metal centers containing non-redox active ions such as Mg^<2+>, Ca^<2+>, Mn^<2+> and Zn^<2+> arc an important bioinorganic motif occurring at the active centers of phosphate ester-processing metalloenzymes. We have systematically studied non-redox active dimetallic complexes by utilizing a biscarboxylate ligand, m-xylylendiamine bis(Kemps triacid imide) (H^2XDK). Zinc-containing homo- and heterodimetallic complexes with diphenylphosphate, [ZnM(XDK){ mu-eta^<12>-(PhO)_2O_2}{eta^1-(PhO_2PO_2}(CH_3OH)_2(H20)]( M = Zn, Co), were prepared in the reactions of [ZnM(XDK)(acac)_2(CH_3OH)_2]with (PhO)_2PO_2H_2. Analogous Mg_2, Mn_2, and Ca_2 complexes. [M_2(XDK){mueta_2-(PhO)_2PO_2){mu_1-(PhO)_2PO_2}(CH_3OH)m(H_2O)n] ( M = Mg, m = 3, n = 1 ; M = Mn, m = n = 2 ; M = Ca, m = 3, n = 1), were obtained. Complexes were characterized by X-ray crystallography, consisting of an asymmetric dimetallic center bridged by XDK and (PhO)_2P0_2, . Variable-temperature ^<3l>p{^1H} … More NMR experiments demonstrated that the terminally coordinated phosphate ester ligand dissociates from the dimetallic center in solution and exchanges with the bridging one. The phosphate ester exchange rate increases in the order Ca^<2+> > Zn^<2+> > Mg^<2+>, providing useful information for understanding phosphate ester-processing metalloenzymes. New dinuclear complexes of Co(II), Cu(I), and Cu(II) were also prepared and their biorelevant reactions were examined.
2. Interactions of carbohydrates with metal ions are vital in biological systems. We have studied the synthesis, characterization, and reactivities of various transition metal complexes with sugar ligands. The mononuclear Co(II) complexes with a heptadentate N-glycoside ligand, [Co(II)((L-Rha or D-Man)_3-tren)]^<2+> showed a molecular recognition property for SO^<2-> anton through chiral inversion of the metal center. Peroxo-bridged dinuclear cobalt (III) comp1ex, [((D-Glc, or Mal)_2-tren)Co(mu-02)Co((D-Glc, or Mal)_2-tren)]X3 (X = Cl, Br), were prepared and characterized by X-ray crystallography to consist of two octahedral Co(III) ions bridged by peroxide. The dinuclear structure is further supported by some hydrogen bonds between the sugar moieties. Interestingly, almost reversible dioxygen binding through the mu-peroxo dimer was monitored by electronic absorption spectral changes upon UV irradiation ; Novel Mn(II)Mn(III)Mn(II) trinuclear complexes with mannopyranose-bridging uri'rs were prepared and characterized by X-ray crystallography. Futhermore, many attempts were made to form biomimetic dimetal centers with tacn-anchored sugar moieties. Less

  • Research Products

    (23 results)

All Other

All Publications (23 results)

  • [Publications] S.Yano,M.Doi,T.Tanase et al: "Trimanganese Complexes with a Linear Mn^<II>Mn^<III>Mn^<II> Assemblage Bridged by Carbohydrates" Chemical Communications (The Royal Society of Chemistry). 997-998 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Tanase, T.Onaka, et al: "Peroxo-bridged Dinuclear Cobalt (III) Complexes Containing N-Glycoside Ligands from Tris (2-aminoethyl) amine and D-Glucose and Their Reversible Dioxygen Binding Properties" Chemical Communications (The Royal Society of Chemistry). 2115-2116 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Tanase, S.Tamakoshi, et al: "Seven-coordinate Manganese (II) Complexes with a Cage-type N-Glycoside Ligand. Configurational Switch Depending on Counter Anions" Inorganica Chimica Acta (Elsevier). 266. 5-7 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Yano, M.Nakagoshi, M.Kato, T.Tanase, et al: "Chiral Inversion around a Seven-coordinate Cobalt Center Induced by an Interaction between Sugars and Sulfate Anions" Inorganic Chemistry (American Chemical Society). 36. 4187-4194 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] D.D.LeCloux, S.J.Lippard: "Synthesis and Characterization of a Novel Class of Dicopper (I) Bis (carboxylate) -Bridge Complexes" Inorganic Chemistry (American Chemical Society). 36. 4035-4046 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Tanase, Y.Yasuda, T.Onaka,S.Yano et al: "Stereochemistry of Nickel (II) Complexes with N-glycosylamine Ligands from 1,3-Diaminopropane and Aldopentoses. Correlation between Configurational Structures and Circular Dichroism Spectra" J.Chem. Soc., Dalton Trans. (The Royal Society of Chemistry). 345-352 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Tanase, T.Inagaki, et al: "Tetranuclear Iron (III) Complexes with Amino Acids Involving a Planar (μ-Oxo) (μ-hydroxo) bis (μ-alkoxo) bis (μ-carboxylato) tetrairon Core" J.Chem. Soc. Delton Trans. (Royal Society of Chemistry). 713-718 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Mikata, T.Tanase, et al: "Structure and Magnetic and Electrochemical Properties of (μ-Aryloxo) bis (μ-carboxylato) diruthenium (III) Complexes" J.Chem. Soc. Dalton Trans. (Royal Society of Chemistry). 1969-1972 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Tanase, N.Takeshita, et al: "(μ-Oxo or hydroxo) bis (μ-carboxylato) diruthenium (III) Complexes with Tris (l-pyrazolyl) borate Face-capping Ligand, Affording Versatile Oxidation States via a Protonation/deprotonation Couple" New J.Chem. (Chemical Society of France). 22. 927-929 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Yano, T.Tanase, et al: "Antifungal Nickel (II) Complexes Derived from Amino Sugars against Pathogenic Yeast, Candida Albicans" J.Inorg. Biochem. (Elsevier). 69. 15-23 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] C.He, S.J.Lippard: "Aminoguanidinium Hydrolysis Effected by a Hydroxo-Bridged Dicobalt (II) Complex as a Functional Model for Arginase and Catalyzed by Mononuclear Cobalt (II) Complexes" J.Am. Chem. Soc. (American Chemical Society). 120. 105-113 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 松本和子、坪村太郎、棚瀬知明、酒井健: "生物無機化学 (S.J.Lippard and J.M.Berg著 日本語訳版)" 東京化学同人, 400 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Tanase, T.Onaka, M.Nakagoshi, I.Kinoshita, K.Shibata, M.Doe.J.Fujii, and S.Yano: "Peroxo-bridged Dinuclear Cobalt(II) Complexes Containing N-Glycoside Ligands from Tris(2-aminoethyl)amine and D-Glucose and Their Reversible Dioxygen Binding Properties" Chem.Commun.2115-2116 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Tanase, S.Tamakoshi, M.Doi, W.Mori, and S.Yano: "Seven-coordinate Manganese(II) Complexes with a Cage-type N-Glycoside Ligand.Configurational Switch Depending on Counter Anions" Inorg.Chim.Acta.266. 5-7 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Yano, M.Doi, S.Tamakoshi, W.Mori, M.Mikuriya, A.Ichimura, I.Kinoshita, Y.Yamamoto, and T.Tanase: "Trimanganese Complexes with a Linear MnIIMnIIIMnII Assemblage Bridged by Carbohydrates" Chem.Commun.997-998. (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Yano, M.Nakagoshi, A.Teratani, M.Kato, T.Onaka, M.Iida, T.Tanase, Y.Yamamoto, H.Uekusa, and Y.Ohashi: "Chiral Inversion around a Seven-Coordinate Cobalt Center Induced by an Interaction between Sugars and Sulfate Anions" Inorg.Chem.36. 4187-4194 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] D.D.LeCloux and S.J.Lippard: "Synthesis and Characterization of a Novel Class of Dicopper(I)Bis(carboxylate)-Bridged Complexes" Inorg.Chem.36. 4035-4046 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Tanase, Y.Yasuda, T.Onaka, and S.Yano: "Stereochemistry of Nickel(II)Complexes with N-Glycoside Ligands from 1,3-Diaminopropane and Aldopentoses. Correlation between Configurational Structures and Circular Dichroism Spectra" J.Chem.Soc., Dalton Trans.345-352 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Tanase, T.Inagaki, Y.Yamada, M.Kato, E.Ota, M.Yamazaki, M.Sato, W.Mori, K.Yamaguchi, M.Mikuriya, M.Takahashi, M.Takeda, I.Kinoshita, and S.Yano: "Tetranuclear Iron(III)Complexes with Amino Acids Involving a Planar(mu-Oxo)(mu-hydroxo)bis(m-alkoxo)bis(m-carboxylato)tetrairon Core" J.Chem.Soc., Dalton Trans.713-718 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Mikata, N.Takeshita, T.Miyazu, Y.Miyata, T.Tanase, I.Kinoshita, A.Ichimura, W.Mori, S.Takamizawa, and S.Yano: "Structure and Magnetic and Electrochemical Properties of (mu-Aryloxo)bis(mu-carboxlato)diruthenium(III)Complexes" J.Chem.Soc., Dalton Trans.1969-1972 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Tanase, N.Takeshita, S.Yano, I.Kinoshita, and A.Ichimura: "(mu-Oxo or hydroxo)bis(mu-carboxylato)-diruthenium(III)Complexes with Tris(1-pyrazolyl)borate Face-capping Ligand, Affording Versatile Oxidation States via a Protonation/deprotonation Couple" New J.Chem.22. 927-929 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Yano, S.Inoue, R.Nouchi, K.Mogami, Y,Shinohara, Y.Yasuda, M.Kato, T.Tanase, Y.Yamamoto, T.Kakuchi, Y.Mikata, and T.Suzuki: "Antifungal Nickel(II)Complexes Derived from Amino Sugars against Pathogenic Yeast, Candida Albicans" J.Inorg.Biochem. 69. 15-23 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] C.He and S.J.Lippar: "Aminoguanidinium Hydrolysis Effected by a Hydroxo-Bridged Dicobalt(II)Complex as a Functional Model for Arginase and Catalyzed by Mononuclear Cobalt(II)Complexes" J.Am.Chem.Soc.120. 105-113 (1998)

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

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Published: 1999-12-08  

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