• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Synthesis of chromium, manganese, and iron porphyrin complexes with less common electron configuration.

Research Project

Project/Area Number 10640551
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionTOHO UNIVERSITY

Principal Investigator

NAKAMURA Mikio  TOHO UNIVERSITY SCHOOL OF MEDICINE PROFESSOR, 医学部, 教授 (20112914)

Co-Investigator(Kenkyū-buntansha) IKEZAKI Akira  TOHO UNIVERSITY SCHOOL OF MEDICINE RESEARCH ASSOCIATE, 医学部, 助手 (80297639)
Project Period (FY) 1998 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 2000: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1999: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1998: ¥1,600,000 (Direct Cost: ¥1,600,000)
Keywordsporphyrins / iron complexes / manganese complexes / NMR spectroscopy / electron configuration / low spin complexes / solvent effect / hydrogen bonding / NMRスペクトル / NMR / ポルフィリン鉄錯体 / ポルフィリン-マンガン錯体 / スピン状態
Research Abstract

The electron configuration of low spin iron (III) porphyrin complexes is generally represented as (d_<xy>)^2(d_<xz>, d_<yz>)^3(d_π type). Recently, We have found that the energy levels of the iron d_<xy> and d_π(d_<xz>, d_<yz>) orbitals are reversed in some complexes with highly nonplanar porphyrin rings, resulting in the formation of the less common (d_<xz>, d_<yz>)^4(d_<xy>)^1(d_<xy> type) ground state. We started the project three years ago to reveal the factors that affect the electronic ground state of low spin iron (III), manganese (III), and chromium (III) porphyrin complexes.
Three factors that could affect the electron configuration of low spin iron (III) are, i) coordination ability of axial ligands, ii) deformation mode of porphyrin ring, and iii) electronic effect of the peripheral substituents. By the extensive studies using ^1H NMR, ^<13>C NMR, and EPR spectra, we have found that i) strong axial ligands such as imidazole and dimethylaminopyridine stabilize the d_π type, while weak axial ligands such as tert-butylisocyanide and 4-cyanopiridine stabilize the d_<xy> type, ii) highly saddle shaped porphyrin rings such as octaethyltetraphenyl-porphyrin stabilize the d_π type, while highly ruffled porphyrin rings such as meso-tetraisopropylporphyrin stabilize the d_<xy> type, iii) porphyrins carrying electron withdrawing substituents at the meso positions stabilize the d_π type, while those with electron donating groups prefer the d_<xy> type.
We have then examined the effect of porphyrin deformation on the electron configuration of manganese (III) porphyrin complexes. However, even by the addition of excess cyanide, the expected bis-adduct was not a sole product. Instead, the mixture of the mono and bis-addcut was observed. Close examination of the coordination reaction has revealed that the ratio, mono vs. bis, chages depending upon the nature of the solvents used. The study to reveal this interesting phenomenon is now in progress.

Report

(4 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • Research Products

    (23 results)

All Other

All Publications (23 results)

  • [Publications] M.Nakamura: "Barriers to inversion of nonplanar ferric porphyrin radical cations : Comparison with the corresponding neutral complexes"Inorg.Chem.. 38. 3126-3131 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] M.Nakamura: "Electron configuration of ferric ions in low spin (dicyano) (meso-tetraprophylporphyrinato)iron(III) complexes"Inorg.Chem.. 38. 3857-3862 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Ohgo: "Bis(tetrahydrofuran)(meso-Tetraethylporphyrinato)bis(tetrahydrofuran)iron(III) perchlorate"Acta Cryst.. C55. 1284-1286 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Ohgo: "Chloro(meso-Tetrapropylporphyrinato)iron(III)"Acta Cryst.. C55. 1817-1818 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ikeue: "Spin distribution in low spin (meso-tetraalkylporphyrinato)iron(III) complexes with (d_<xz>,d_<yz>)^4 (d_<xy>)^1 configuration"J.Am.Chem.Soc.. 122. 4068-4076 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ikeue: "Direct observation of conformers caused by the difference in ligand orientation in low spin iron(III) porphyrin complexes"Chem.Lett.. 342-343 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] A.Ikezaki: "Chem.Lett."Formation and characterization of mono-imidazole ligated (meso-tetramesitylporphyrinato) iron(III) complexes : Model for cytochromes c. 994-995 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] A.Ikezaki: "J.Inorg.Biochem."Formation of m-oxo dimer by the reaction of (meso-tetraphenylporphyrinato)iron(III) with various imidazoles(印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ikeue: "High spin (meso-tetraalkylporphyrinato)iron (III) complexes as studied by X-ray crystallography, EPR, and dynamic NMR spectroscopy"Inorg.Chem.. 38. 1276-1281 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] M.Nakamura: "Barriers to Inversion of Nonplanar Ferric Porphyrin Radical Cations : Comparison with the Corresponding Neutral Complexes."Inorg.Chem.. 38. 3126-3131 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] M.Nakamura: "Electron Configuration of Ferric Ions in Low Spin (Dicyano)(meso-tetraarylporphyrinatoiron(III) Complexes."Inorg.Chem. 38. 3857-3862 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Ohgo: "Bis (tetrahydrofuran)(meso-tetraethylporphyrinato)iron (III) perchlorate"Acta Cryst. C55. 1284-1286 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Ohgo: "Chloro (meso-tetrapropylporphyrinato) iron (III)"Acta Cryst. C55. 1817-1818 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ikeue: "Direct Observation of Conformers Caused by the Difference in Ligand Orientation in Low Spin Iron (III) Porphyrin Complexes"Chem Lett.. 342-343 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ikeue: "Spin Distribution in Low Spin (meso-Tetraalkylporphyrinato) iorn (III) Complexes with (d_<xz>, d_<yz>)^4(d_<xy>)^1 Configuration."J.Am.Chem.Soc.. 122. 4068-4076 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] A.Ikezaki: "Formation and Characterization of Monoimidazole Ligated (meso-Tetramesitylporphyrinato) iron (III) Complexes : Model for Cytochromes c'."Chem.Lett.. 994-995 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Ohgo: "Formation of Pure Intermediate Spin Complexes in Highly Nonplanar Iron (III) Porphyrins"Chem.Commun. 1989-1990 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Ohgo: "Bis (tetrahydrofuran)(meso-tetraisopropylporphyrinato)-iron (III) Perchlorate"Acta Cryst. C57. 233-234 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] A.Ikezaki: "Formation and characterization of mono-imidazole ligated (meso-tetramesitylporphyrinato) iron (III) complexes : Model for cytochromes c'"Chem.Lett..

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Ikezaki: "Formation of μ-oxo dimer by the reaction of (meso-tetraphenylporphyrinato) iron (III) with various imidazoles"J.Inorg.Biochem..

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Nakamura,T.Ikeue,A.Ikezaki,Y.Ohgo,H.Fujii:: "Electron Configuration of Ferric Ions in Low Spin (Dicyano)(meso-tetraarylporphyrinato-iron(III) Complexes."Inorganic Chemistry. 38. 3857-3862 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Ikeue,Y.Ohgo,T.Saitoh,M.Nakamura,H.Fujii,M.Yokoyama:: "Spin Distribution in Low Spin (meso-Tetraalkylporphyrinato)iorn(III) Complexes with (d_<xy>,d_<yz>)^4(d_<xy>)^1 Configuration."Journal of the American Chemical Society. 122. (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Nakamura et al.: "High-spin(meso-tetraalleylporphyrinato)iron(III)complexes ……" Inorganic Chemistry. 38. (1999)

    • Related Report
      1998 Annual Research Report

URL: 

Published: 1998-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi