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The Rotational Orientation Angles of Axial Ligands in Low-Spin Fe(III) Heme Complexes As Determined from Frozen-Solution Samples

Research Project

Project/Area Number 63571026
Research Category

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

Allocation TypeSingle-year Grants
Research Field Physical pharmacy
Research InstitutionTeikyo University

Principal Investigator

SATO Mitsuo  Biophys. Div., Fac. Pharm. Sci., Prof., 薬学部, 教授 (70101714)

Co-Investigator(Kenkyū-buntansha) 藤原 美香  帝京大学, 薬学部, 教務職員
Project Period (FY) 1988 – 1989
Project Status Completed (Fiscal Year 1989)
Budget Amount *help
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1989: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1988: ¥1,400,000 (Direct Cost: ¥1,400,000)
KeywordsLow-spin Fe(III) heme complex / Rotational orientation of rhombic field / Rotational orientation of axial ligand / Iron-57 hf splitting / Relative orientations of g and hf tensors / Pー450モデル錯体 / P-450モデル錯体 / 軸配位子の回転配向
Research Abstract

Hyperfine (hf) splittings due to the ^<57>Fe nucleus (I=1/2) have been observed in frozen-solution ESR measurements on a series of low-spin Fe(III) heme complexes, Fe(TPP)L_1L_2, where TPP =tetraphenylporphine dianion, L_1 = RS^-, L_2 = MeOH, DMF, and RSH, and R = Et, n-Pr, i-Pr, n-Bu, s-Bu, and t-Bu. The hf splitting (A_<(i)>) values of the g_i absorption peaks (i = X, Y, Z) are analyzed within the framework of a low-symmetry (C_2) crystal field model to determine the rotational orientation angle (phi) of the axes of rhombic component field and that (phi_l) of the axial thiolato ligand plane (Fe-S-C plane) with the approximation of phi_l = phi. It is found that phi_l varies from 6 to 37゚ depending upon the thiolato ligand (RS^-), the 6th axial ligand (L_2), and the solvent system (CH_2Cl_2 - MeOH, DMF-MeOH, or CH_2Cl_2-RSH), but with no clear correlation between phi_l and RS^-. However, phi_l correlates well with the energy splittings in the three t_2 orbitals: phi_l increases as the tetragonal splitting decreases or as the rhombic splitting and crystal field rhombicly increase. These results suggest that two major factors, namely, steric and electronic effects, influence the axial ligand orientation. The observed angles phi_l = 6-37゚ are the results of the two effects.

Report

(3 results)
  • 1989 Annual Research Report   Final Research Report Summary
  • 1988 Annual Research Report
  • Research Products

    (20 results)

All Other

All Publications (20 results)

  • [Publications] M.Sato: "Electron Spin Resonance Studies of Low-Spin Ferric Heme Complexes in Frozen Solutions.Iron-57 Hyperfine Splittings and the Angular Orientation of Rhombic Field" Nippon Kagaku Kaishi. 522-530 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] A.Tohara: "Photoreduction of Hydroxotetramesitylporphinatoiron(III)in Aromatic Hydrocarbons and the Concurrent Generation of Hydroxyl Radical" Chem.Let.,. 153-156 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] N.Kobayashi: "Mossbauer and ESR Spectroscopy of Tetranitro-and Tetraaminophthalocyaninatoiron" Makromol.Chem.,. 10. 1-4 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Itoh: "Deoxygenation of Oxiran Compounds to Olefins by [Fe_4S_4(SC_6H_5)_4]^<2-> in the Presence of NaBH_4" Tetrahedron Let.,. 30. 6387-6388 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Sato: "Rotational Angular Orientation of Axial Thiolato Ligand in Low-Spin P-450 Model Complexes" J.Pharmacobio-Dyn.,. 13. s-5 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] J.Takeda: "A New Synthesis of Octaarylporphyrins:Naturally Occuring Porphyrin Mimics" Chem.Pharm.Bull.,. 38. 264-266 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Sato, T. Otsuka, T. Ohya: "Electron Spin Resonance Studies of Low-Spin Ferric Heme Complexes in Frozen Solutions. Iron-57 Hyperfine Splittings and the Angular Orientation of Rhombic Crystal Field" Nippon Kagaku Kaishi, 522, 1988.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] A. Tohara, M. Sato: "Photoreduction of Hydroxotetramesitylporphinato)iron(III) in Aromatic Hydrocarbons and the Concurrent Generation of Hydroxyl Radical" Chemistry Letters, 153, 1989.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Itoh, T. Nagano, M. Sato, M. Hirobe: "Deoxygenation of Oxiran Compounds to Olefins by [Fe_4S_4(SC_6H_5)_4]^<2-> in the Presence of NaBH_4" Tetrahedron Letters, 30, 6387, 1989.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] N. Kobayashi, H. Konami, T. Ohya, M. Sato, H. Shirai: "Mossbauer and ESR Spectroscopy of Tetranitro- and Tetraaminophthalocyaninatoiron" Makromol. Chem., 10, 1, 1989.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Sato, T. Ohya: "Rotational Angular Orientation of Axial Thiolato Ligand in Low-Spin P-450 Model Complexes" J. Pharmacobio-Dyn., 13, s-5, 1990.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] J. Takeda, T. Ohya, M. Sato: "A New Synthesis of Octaarylporphyrins: Naturally Occurring Porphyrin Mimics" Chem. Pharm. Bull., 38, 264, 1990.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Ohya, J. Takeda, N. Kobayashi, M. Sato: "Bonding Character in Tetracoordinate (Phthalocyaninato) - iron(II) Complexes with Electron-Releasing Substituents As Studied by Mossbauer Spectroscopy" Inorg. Chem.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] N.Kobayashi: "Mossbauer and ESR Spectroscopy of Tetranitro-and Tetraaminophthalocyaninatoiron" Makromol.Chem.,. 10. 1-4 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Itoh: "Deoxygenation of Oxiran Compounds to Olefins by[Fe_4S_4(SC_6H_5)_4]^<2-> in the Presence of NaBH_4" Tetrahedron Let.,. 30. 6387-6388 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] M.Sato: "Rotational Angular Orientation of Axial Thiolato Ligand in Low-Spin p-450 Model Complexes" J.Pharmacobio-Dyn.,. 13. s-5 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] J.Takeda: "A New Synthesis of Octaarylporphyrins:NaturallyOccuring Porphyrin Mimics" Chem.Pharm.Bull.,. 38. 264-266 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Ohya: "Bonding Character in Tetracoodinate(Phthalocyaninato)Iron(II)Complexes with Electron-Releasing Substituents" Inorg.Chem.,in press.

    • Related Report
      1989 Annual Research Report
  • [Publications] 佐藤三男: 日本化学会誌. 522-530 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] A.Tohara: Chemistry Letters. 153-156 (1989)

    • Related Report
      1988 Annual Research Report

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Published: 1988-04-01   Modified: 2016-04-21  

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