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

CHARACTERIZATION OF PHOTOREACTION PRODUCTS AND PHOTOREACTION MECHANISM

Research Project

Project/Area Number 03640521
Research Category

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

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionKOCHI UNIVERSITY

Principal Investigator

YASUI Takaji  KOCHI UNIVERSITY,FACULTY OF SCIENCE,PROFESSOR, 理学部, 教授 (20028161)

Project Period (FY) 1991 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1993: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1992: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1991: ¥900,000 (Direct Cost: ¥900,000)
KeywordsCOBALT(III) COMPLEX / DIAMINODICARBOXYLIC ACID COMPLEX / OPTICALLY ACTIVE COMPLEX / PYOTOLYSIS / CARBON-13 NMR / CIRCULAR DICHROSIM / X-RAY ANALYSIS / ジアミノカルボン酸錯体 / 円偏向二色性 / アミノカルボン酸錯体 / コバルト錯体の立体化学 / CDスペクトルと絶対配置 / 炭素核NMR / コバルト錯体の光反応 / コバルト-炭素結合錯体 / コバルト錯体 / CDスペクトル / 光反応化学 / コバルトー炭素間結合錯体
Research Abstract

The cobalt (III) complexes (alpha, beta-1, and beta-2 [Co(eddp)(en)X, beta-[Co(tndp)(en)X, and alpha-[Co(Me_2eddp)(en)]X) containing diaminodicarboxylates [^-OCOCH_2CH_2NR(CH_2) nNRCH_2CH_2COO^- : eddp(R=H, n=2) ; tndp (R=H, n=3) ; Me_2eddp (R=CH_3, n=2)] as quadridentate ligands and ethylenediamine [NH_2CH_2CH_2NH_2 : en] as a bidentate ligand were newly prepared and optically resolved. The geometrical structures and absolute configurations were determined on the basis of the absorption, CD, C-13 NMR spectral date and the crystallographic date.
The aqueous solution of racemic and optically active complexes were irradiated by a 400W high-pressure mercury lamp (internal irradiating lamp) at ca, 5゚C for 40-60 min. The resulted solution were column-chromatographed and the desired complexes containing cobalt(III)-carbon bond were obtained from orange and purple eluates. The C-13 NMR spectra of these orange and purple complexes exhibited characteristic resonance peaks at very high magnetic field (at ca.-5 ppm), which are assigned to the carbanion-carbon coordinated to a cobalt(III) ion.
The geometrical structures and absolute configurations of the optically active complexes containing Co-C bond were determined on the basis of the absorption, CD, C-13 NMR spectral date and the crystallographi date. The photolyses of the optically active LAMBDA-alpha, LAMBDA-beta-1, and LAMBDA-beta-2 [Co(eddp)(en)]X produced stereospecifically Co-C bond isomers having LAMBDA-alpha, DELTA-alpha, and LAMBDA (or DELTA)-beta configurations, respectively, and the photolyses of DELTA-beta-[Co(tndp)(en)]X and LAMBDA-alpha-[Co(Me_2eddp)(en)]X produced LAMBDA (or DELTA)-beta and LAMBDA-alpha Co-C bond isomers, respectively.
The present results suggested that the photodecarboxylation occurred stereospecifically on one of the two carboxy1 groups of the coordinated diaminodicarboxyate.

Report

(4 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • 1991 Annual Research Report
  • Research Products

    (6 results)

All Other

All Publications (6 results)

  • [Publications] Tomoharu Ama: "An optically active cobalt(III) complex containing Co-C bond prepared by the photolysis of optically active (ethylenedi-amine)(ethylenediamine-N,N'-dipropionato) cobalt(III) complex ion." Chemistry Letter. 1991. 1543-1546 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hiroshi Kawaguchi: "The isomerism of the (ethylenediamine-N,N'-dipropionato)-(ethylenediamine) cobalt(III) ion and its stereoselective isomerization reaction." Bulletin Chemical Society of Japan. 65. 175-179 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Tomoharu Ama, Nobukatsu Hasegawa, Hirosi Kawaguchi, and Takaji Yasui: "An Optically Active Cobalt(III) Complex Containing Co-C Bond Rrepared by the Photolysis of Optically Active (Ethylenediamine)(entylenediamine-N,N'-dipropionato)-cobalt (III) Complex Ion." Chem.Lett.1991(9). 1543-1546 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hiroshi Kawaguchi, Noboru Maruyama, Tomoharu Ama, and Takaji Yasui: "The Isomerism of the (Ethylenediamine-N,N'-dipropionato)(enthylenediamine) cobalt(III) Ion and its Stereo-selective Isomerization reaction." Bull, Chem.Soc.Jpn.65(1). 175-179 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Ama,N.Hasegawa,H.Kawaguchi,and T.Yasui: "An optically active cobalt(III)complex containing CoーC bond prepared by the photolysis of optically active(ethylenediamine)(ethylenediaminen,N'ーdipropionato)cobalt(III)complex ion." Chemistry Letters(Chem.Lett.). 1991. 1543-1546 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] H.Kawaguchi,N.Maruyama,T.Ama,and T.Yasui: "The isomerism of the(ethylenediamineーN,N'ーdipropionato)(ethylendiamine)cobalt(III)ion and its stereoselective isomerization reaction." Bulletin of the Chemical Society of Japan(Bull.Chem.Soc.Jpn.). 65. 175-179 (1992)

    • Related Report
      1991 Annual Research Report

URL: 

Published: 1991-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi