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配位原子への水素結合による金属錯体の機能制御

Research Project

Project/Area Number 12020237
Research Category

Grant-in-Aid for Scientific Research on Priority Areas (A)

Allocation TypeSingle-year Grants
Research InstitutionOsaka University

Principal Investigator

上山 憲一  大阪大学, 大学院・理学研究科, 教授 (80093376)

Project Period (FY) 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 2000: ¥1,700,000 (Direct Cost: ¥1,700,000)
KeywordsNH-S水素結合 / 金属-硫黄結合 / Hg硫黄錯体 / Cu硫黄錯体 / Fe硫黄錯体 / P-450モデル
Research Abstract

金属酵素の反応性変化は主に『配位原子への水素結合』によることをモデル錯体の研究から見出しきたが、その延長上に、蛋白質などの構造変化が、水素結合のインターフェイスを使い、金属イオンのトランス位の配位子の求核性の変化に連動し、非線形的に反応を制御している機構の解明につながる研究がある。この配位子の構造変化で求核性の変化を起こしうる簡単な配位子を使って錯体を合成し、配位子の水素結合による求核性の変化で錯体の機能が変化することを調べた。チトクロームP-450の活性中心の金属イオンにおける『水素結合によるその中間体の安定化』と、Hg(II)イオンの2配位と4配位錯形成での構造変化による機能制御に関して新しい知見が得られたので報告する。
金属錯体の配位子が構造変化することによって配位原子に水素結合を形成したり、切断が可能な配位子として2-t-BuNHCOC_6H_4SHとその脱プロトン化した(NEt_4)(S-2-t-BuNHCOC_6H_4)を合成し、それぞれの結晶構造を決定した。その結果、前者はSH-O=Cの水素結合をもち、後者はS-HN水素結合をもつことがわかり、芳香環とアミド面の間で180°の回転が起こった構造変化をしていることがわかった。金属-硫黄結合が共有結合性の2配位錯体、Hg(S-2-t-BuNHCOC_6H_4)_2では水素結合を作らないことがわかり、一方、同じ配位子をもつ4配位錯体、(NEt_4)_2[Hg(S-2-t-BuNHCOC_6H_4)_4]では180゜回転してNH-S水素結合を作り、Hg-S結合はイオン性になっているとわかった。この性質は、同じd^<10>錯体の3配位錯体、(NEt_4)[Cu(S-2-t-BuNHCOC_6H_4)_3]やd^6の4配位錯体、(NEt_4)_2[Fe^<II>(S-2-t-BuNHCOC_6H_4)_4]もNH-S水素結合を作ることから、金属-硫黄の結合性に依存した硫黄原子の状態でこの水素結合は形成する場合としない場合があり、同時に配位子の構造に連動できることがわかった。

Report

(1 results)
  • 2000 Annual Research Report

Research Products

(16 results)

All Other

All Publications

  • [Publications] N.Ueyama,Jiro Takeda,Yusuke Yamada,Taka-aki Okamura and Akira Nakamura: "Dinuclear Calcium Complexes with Intramolecularly NH-O Hydrogen-Bonded Dicarboxylate Ligand."Inorg.Chem.. 38. 475-478 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Onoda,Y.Yamada,M.Doi,T.Okamura,N.Ueyama: "Dinuclear Calcium Complex with Weakly NH-O HY drogen Bonded Sulfonate Ligands"Inorg.Chem.. 40. 516-521 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] N.Ueyama,H.Kozuki,M.Doi,Y.Yamada,K.Takahashi,A.Onoda,T.Okamura,H.Yamamoto: "Secure Binding of Alternately Amidated Poly(acrylate) to Crystalline Calcium Carbonate by NH-S Hydrogen Bond"Macromolecules. (in press). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] Y.Nakayama,K.Watanabe,N.Ueayama,A.Nakamura,A.Harada: "Titanium Complexes Having Chelating Diaryloxo Ligands Bridged by Tellurium and Their Catalytic Behavior in the Polymerization of Ethylene"Organometallics. 19. 2498-2503 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] W.-Y,Sun,B.-L.Fei,T.Okamura,Y.-A.Zhang,T.Ye,W.-X.Tang,N.Ueyama: "Structures of [M(cbim)_4(NO_3)_2][M=Cd(II), Co(II) and Ni(II) ; cbim=4'-Cyanobenzyl-1-imidazole] in the Solid State and in Solution"Bull.Chem.Soc.Jpn.. 73. 2733-2738 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] W.-Y.Sun,J.Fan,T.Okamura,N.Ueyama: "Synthesis and Structural Characterization of a New One-dimensional Chain Coordination Polymer of Copper(II) with Diethylenetriamine and 1,3-Bis(imidazol-1-ylmethyl)-5-methylbenzene"Inorg.Chem.Commun.. 3. 541-544 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] W.-Y.Sun,J.Xie,T.Okamura,C.-K.Huang,N.Ueyama: "Novel Tripodal Chelating Ligand for Appending and Encapsulating Metal Ions. Crystal Structure of a Parachute-like Hydrogen Bonded Complex"J.Chem.Soc.Chem.Commun.. 1429-1430 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] W.-Y.Sun,Y.-A.Zhang,T.Okamura,T.Ye,N.Ueyama: "Synthesis and Crystal Struture of a New Two-Dimensional Coordination Polymer, {[Co^<II>(imbz)_2]H_2O}_n [imbz=4'-(Imidazol-1-ylmethyl)benzoate Anion]"Chem.Lett.. 1222-1223 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] N.Ueyama,Y.Yamada,H.Kozuki,T.Okamura: "Strontium Carnonate Crystals Strongly Bound by Poly(Carboxylate) ligand Supported by NH-O Hydrogen Bond between Carboxylate and Neighboring Amide NH Groups."高分子論文集. 57. 228-232 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Ueno,N.Nishikawa,S.Moriyama,S.Adachi,K.Lee,T.Okamura,N.Ueyama: "Role of the Invariant Peptide Fragment Froming NH-S Hydrogen Bonds in the Active Site of Cytochrome P-450 and Chloroperoxidase : Synthesis and Properties of Cys-Containing Peptide Fe(III) and Ga(III) (Octaethylporphinato) Complexes as Models."Inorg.Chem.. 38. 1199-1210 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] Y.Nakayama,H.Saito,N.Ueyama,and A.Nakamura: "Isomerization and a-H Elimination of Dialkyltungsten Complexes Stabilized by a Sulfur-Bridged Chelating Diaryloxo Ligand."Organometallics. 18. 3149-3158 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] N.Ueyama,M.Inohara,A.Onoda,T.Ueno,T.Okamura,and A.Nakamura: "Protection of Proton-Initiated Ligand Dissociation from Hg(II) complexes with Bulky Cholyl Amode Arenethiolate by NH-S Hydrogen Bonding in an Aqueous Micellar Solution."Inorg.Chem.. 38. 4028-4031 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] Y.Nakayama,K.Miyamoto,N.Ueyama,and A.Nakamura: "Synthesis, Structure and Catalytic Activity of a Seven-Coordinate Titanium(IV) Tris(pyridine-2-thiolate) Complex."Chem.Lett.. 391-392 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.-K Liu,W.-Y.Sun,W.-X.Tang,T.Yamamoto,N.Ueyama: "Self-Assembly of the First Copper(II) Infinite 2D Network with Large Cavities Formed between the Two Adjacent Layers"Inorg.Chem.. 38. 6313-6316 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.Oku,N.Ueyama,A.Nakamura: "Dioxomolybdenum(VI) and Dioxotungsten(VI) Structure with Mono (Dithiolato) Coordination : Crystal Structures, Properties and Reactivity of [{M^<VI>O_2(dithiolato)}_2(μ-O)]^<2->(M=Mo and W) Complexes"Bull.Chem.Soc.Jpn.. 72. 2261-2270 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Nakamura,N.Ueyama,K.Yamaguti: "Organometallic Conjugation"Kodansya Ltd.and John Willey & Sons,Inc.. (2001)

    • Related Report
      2000 Annual Research Report

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Published: 2000-03-31   Modified: 2016-04-21  

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