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Synthesis and design of paramagnetic metal complexes containing stable radicals and their spectroscopic study

Research Project

Project/Area Number 06453049
Research Category

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

Allocation TypeSingle-year Grants
Research Field Inorganic chemistry
Research InstitutionOsaka University

Principal Investigator

KAIZAKI Sumio  Osaka University, Dept.Chem., PROFESSOR, 理学部, 教授 (20089874)

Co-Investigator(Kenkyū-buntansha) FUYUHIRO Akira  Osaka University, Dept.Chem.RESEARCH ASSISTANT, 理学部, 助手 (90156951)
YAMANARI Kazuaki  Osaka University, Dept.Chem.ASSOCIATE PROFESSOR, 理学部, 助教授 (40116124)
Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 1995: ¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 1994: ¥3,800,000 (Direct Cost: ¥3,800,000)
KeywordsStable Radical / Radical Complexes / Spin-Forbidden Transition / Radical-metal Interaction / クロム(III)錯体 / スピン交換相互作用 / 磁気的相互作用
Research Abstract

This research aims at versatility and fine-tuning of the exchange coupling between metal complexes and radical ligands together with electronic and magnetic interaction between the ligand field and radicals as well as the reactivity of radical complexes in solutions for the primary purpose of synthesis and design of paramagnetic metal complexes containing radical ligands.
Firstly, we have revealed the behavior or the d electron state due to the subtle change of the ligand field such as the solvent effects as observed for the NMR and solvatochromism as well as anomalous trigonal field splitting due to anisotropic pi bonding. Furthermore, we explored the steric effect due to weak intramolecular interactions such as hydrogen bond and CH/pi interaction. These studies are the important and basic information to examine the coordination bond between the metal and radical, especially between the d orbital and pi^* orbital (SOMO)
Secondarily, radical complexes of paramagnetic Cr(III) and Ni(II) metal such as [Cr(acac)_2(NIT2-py)]+or[Ni(dbm)_2(NIT2-py)](dbm=dibenzoylmethane) and those of diamagnetic Co(III) metal such as trans-[Co(acac)_2(X)(NIT4+py)]^n(X=PPh_3 : n=1+ ; NO_<-2> : n=0)) and trans-[Co(acac)_2(P(Ph_3))(4-NH_2tempo)]+have been prepared. Their stability and magneto-optic properties such as the intensity enhancement of the spin-forbidden transitions were examined. The X-ray structure analysis of trans-[Co(acac)_2(PPh_3)(NIT4-py)]+confirmed the pyridine coordination mode. These data will be an important clue to accomplish the present purpose and valuable for the chemistry for radical complexes.

Report

(3 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] Narumi Sakagami: "Crystal Structures of the (Ethylenediamine-N,N'-dipropionato) (ethylenediamine) cobalt(III) Isomers." Bull. Chem. Soc. Jpn.67. 680-686 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Sumio Kaizaki: "Structural Characterization of Octahedral Metal Complexes of [MX_3(py)_3] Type with Three Pyridines as Rerealed by ^2H NMR Spectra" Inorg. Chim. Acta. 218. 179-184 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Yukiko Terasaki: "Solvent-dependent ^2H Nuclear Magnetic Resonanee Spectra and Solvatochromism in Ligand-fleld Absorption Bands of C : S-[CrF_2N_4]-type Complexes with Triethylene-tetramine,Pyridine or 2,2'-Bipyridine." J. Chem. Soc. Dalton Trans.1995. 2837-2841 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Narumi Sakagami: "Syntheses and Characterization of (Diamine-N,N'-dicarboxy-lato) chrometa (III) Dinuclear Conplexes Bridged by Ryrazole-3,5-dicarboxy lata : X-ray Structures of NaICr_2 (edda)_2-(μ-pzdc)]・5H_2O and NaICr_2 (trdda)_2 (μ-pzdc)]・3H_2O" Inorg. Chem.35. 683-688 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Kazuaki Yamanari: "CH/π Interaction in Linkage Isomers of Bis (2,2'-bipyridine) ruthenium (II) Complexes with pyrimidine-2-thione and Related Ligands" Chem. Lett.1996. 35-36 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] N.Sakagami, T.Yasui, H.Kawaguchi, T,Ama and S.Kaizaki: "Crystal Structure of the (Ethylenediamine-N,N'-dipropionato)(ethylenediamine) cobalt(III) Isomers" Bull.Chem.Soc.Jpn.67. 680-686 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] S.Kaizaki and J.I.Legg: "Structural Characterization of Octahedral Metal Complexes of [MX3(py)3] Type with Three Pyridines as Revealed by 2HNMR Spectra" Inorg.Chim.Acta.218. 179-184 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Terasaki and S.Kaizaki: "Solvent-dependent 2H NMR spectra and solvatochromism in ligand field bands of cis-[CrF2N4] type complexes with trimethylene tetramine pyridine and 2,2'-bipyridine" J.Chem.Soc.Dalton Trans.1995. 2837-2841 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] N.Sakagami, M.Nakahanada K.Ino, A.Hioki and S.Kaizaki: "Syntheses and Characterization of Diamine-N,N'-dicarboxylato Chromate(III) Dinuclear Complexes Bridged by Pyrazol-3,5-di-carboxylate : X-ray Structures of Na[Cr2(edda)2(m-pzdc)]H2O and Na[Cr2(trdda)2(m-pzdc)]H2O" Inorg.Chelm.35. 683-688 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Yamanari T.Nozaki A.Fuyuhiro and S.Kaizaki: "Ch/p Interaction in Linkage Isomers of Bis (2,2'-bipyridine)ruthenium(II) Complexes with Pyrimidine-2-thione and Related Ligands" Chem.Lett.1996. 35-36 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Yukiko Terasaki: "Solvent-dependent ^2H Nuclear Magnetic Resonance Spectra and Solvatochromism in Ligand-field Absorption Bands of Cis-[CrF_2N_4]-type complexas with Triethylenetetramine,Pyridine or 2,2^1-Bipyridine." J.Chem.Soc.Dalton Trans.1995. 2837-2841 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Takashi Fujihara: "New Herero^- and Homo-metallic Dihydroxo-bridged Dinuclear Complexes of Cobalt(III) and Chromium(III) : Synthesis,Spectroscopy and Crystal Structures." J.Chem.Soc,Dalton Trans.1995. 1813-1821 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Takashi Fujihara: "Base Hydrolysis in Homometallic Dinuclear Chromium (III) Complexes bridged by Hydroxide and Carboxylate." J.Chem.Soc,Dalton Trans.1995. 1823-1831 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Kazuaki Yamanari: "CH/π Interaction in Linkage Isomers of Bis(2,2′-bipyridine) ruthenium(II) Complexea with Pyrimidine-2-thione and Related Ligands." Chem.Lett.1996. 35-36 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] Narumi Sakagami: "Syhtheses and Characterization of (Diamine-N,N′-dicarboxylato) chromate(III) Dinuclear cpmplexes Bridged by Pyrazole-3,5-dicarboxylate : X-ray Structures of Na[Cr_2(edda)_2(μ-pzdc)]・5H_2O and Na[Cr_2(trdda)_2(μ-pzdc)]・3H_2O." Inorg.Chem.35. 683-688 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] Narumi Sakagami: "Crystal Structures of the (Ethylenediamine-N,N′-dipropionato)-(ethylenediamine)cobalt(III)Isomers." Bull.Chem.Soc.Jpn.67. 680-686 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Sumio Kaizaki: "Structural Charaterization of Octahedral Metal Complexes of[MX_3(PY)_3]Type with Three Pyridines as Revealed by ^2H NMR Spectra." Inorg.Chim.Acta. 218. 179-184 (1994)

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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