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Design and Syntheses of Paramagnetic Dinuclear Metal Complexes Inducing Significant Cooperative Effects and Their Multinuclear NMR Study

Research Project

Project/Area Number 02453040
Research Category

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

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionOsaka University

Principal Investigator

KAIZAKI Sumio  Dept. Chem., Fac. Sci., Osaka Univ. Prof., 理学部, 教授 (20089874)

Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥6,800,000 (Direct Cost: ¥6,800,000)
Fiscal Year 1991: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1990: ¥5,400,000 (Direct Cost: ¥5,400,000)
KeywordsCr (III) dinuclear omplex / Spin-forbidden d-d Transition / Circular Dichroism / Magnetic circular Dichroism / Multinuclear NMR / Magnetic Susceptibility / exchange interaction / Cooperative Effect
Research Abstract

1. Preparation of new dinuclear complexes :
(1) New dinuclear complexes of[Cr_2 (X)_2 (acac)_2] type (acac=acetylacetonato) with bridging ligands such as oxalato, fluoro, 4, 5-imidazoledicarboxylato, 3.5pyrazinedicarboxylato, pyrazole (hydroxo) were synthesized.
(2) A systematic synthetic route to dinuclear complexes ( (N-N)_2 Cr(OH)(RCOO)Cr(nta)]^+((N-N)=(NH_3)_2, ethylenediamine, R, R-cyclohexanediamine ; nta=nitrilotriacetato ; R=CH_<>Cl, H, C_6H_5, CH_3) was established.
(3) New dihydroxo dinuclear complex[Cr_2(OH)_2 ( (R, R)-chxn)_4]^<4+> and hydroxoaqua dinuclear complexes[Cr_2(OH)_2(H_2O)_2 ( (R, R)-chxn)_4]^<4+>, [Cr_2(OH)(H_2O) (edtrp)_2] and[Cr_2(OH)(H_2O) ( (S)-pdtrp)_2] were prepared and characterized.
2. X-ray structural analyses :
The X-ray structural analyses were performed for two isomorphous crystals[(tn)_2Cr(OH)_2M(nta)]Cl-1.5H_2O(M=Cr, Co), and their molecular structures were compared with each other with respect to the difference in bond lengths and bond angles between central metal ions.
3. NMR spectra :
For[(N-N)_2Cr(OH)_2M(nta)]^+ (M=Cr(III), Co(III)) ; ((N-N)=(NH_3)_2, ethylenediamine, R, Rcyclohexanediamine, 2, 2'-bipyridine ; nta=nitrilotriacetato), ^1H-, ^2H-NMR spectra were observed and examined in view of the influence from the paramagnetic CR (III)ion in[Cr-Cr)and[Cr-Col complexes. ^2HNMR spectra of the bridging ligands in[(N-N)_2Cr(OH) (CD_3COO)Cr (nta)]^+ were measured.
4. Magnetic susceptibility measurements :
The construction of a Faraday apparatus for automatic magnetic susceptibility measurement was completed. The temperature dependent magnetic susceptibility for new dinuclear CR (III) complexes obtained throughout the present research project term was measured and their magnetic interactions were discussed in relation with the electronic properties of the bridging ligands.

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (5 results)

All Other

All Publications (5 results)

  • [Publications] Manabu Nakahanada: "Syntheses and X-Ray Structures of Novel Phenoxo Bridged Binuclear Complexes:Bis(μ-phenoxo)bis[bis(acetylacetonato)chromium(III)]Complex and Its Para Substituted Phenoxo Analogues" Inorg.Chem. 31. (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Manabu Nakahanada: "Syntheses and X-Ray Structures of Novel Phenoxo Bridged Binuclear Complexes : Bis (mu-phenoxo) bis-[bis (acetylacetonato) chromium (III)] complex and its Pars Substituted Phenoxo Analogues." Inorg. Chem.31. (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Manabu Nakahanada: "Syntheses and XーRay Structures of Novel Phenoxo Bridged Binuclear Complexes:Bis(μーphenoxo)bis[bis(acetylacetonato)ーchromium(III)]Complex and Its Para Substituted Phenoxo Analoques" Inorg. Chem.31. (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] Sumio Kaizaki: "Elucidation of Shimura's Reduction Parameter for the First Ligand Field Band Components of Cobalt(III)and Chromium(III)Mixed Ligand Complexes" Bull.Chem.Soc.Jpn. 63. 3198-3202 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Sumio Kaizaki: "SolventーDependent Deuteron NMR Spectra and Solvatochromism in Ligand Field Absorption Bands for transー[CrX_2(3,2,3ーtet)]^+:Correlation with the Angular Overlap Model Parametrization" Inorg.Chem.29. 4960-4964 (1990)

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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