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Stereochemistry of alkyl pendant ligands coordinated to metal complexes and its effect on reactivity

Research Project

Project/Area Number 04640583
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 InstitutionKumamoto University

Principal Investigator

GOTO Masafumi  Kumamoto University, Faculty of Pharmaceutical Sciences, Professor, 薬学部, 教授 (50080180)

Co-Investigator(Kenkyū-buntansha) KUROSAKI Hiromasa  Kumamoto University, Faculty of Pharmaceutical Sciences, Asistant Professor, 薬学部, 助手 (70234599)
MORI Hiromasa  Kumamoto University, Faculty of Pharmaceutical Sciences, Associate Professor, 薬学部, 助教授 (40040315)
Project Period (FY) 1992 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1993: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1992: ¥1,500,000 (Direct Cost: ¥1,500,000)
KeywordsFe complexes / cobalt(III)complexes / platinum(II) complexes / dehydrogenation / hydrophobic interaction / NMR / X-ray crystallography / alkyl pendant ligand / N-ベンジルエチレンジアミン / 配位原子 / アルキルペンダント / 金属錯体
Research Abstract

The Co, Fe, and Pt complexes containing the alkyl pendant ligands were synthesized and their characteristics were clarified.
1. N-Alkyl substituents of [Co^<III>(CN)_4L]^<3+> or [Co^<III>(NH_3)_4L]^<3+>(L=Eten or Been) took pseudoequatorial disposition in regard with the chalete ring and anti-conformation. N-Benzyl group of [Pt(bpy)L]^<2+> and [Pt(bpy)L]^<2+> took pseudoaxial disposition and a intramolecular hydrophobic interaction occurred between the aromatic rings in aqueous solution. Substitution of N-benzyl with N-naphthylmethyl and N-anthrylmethyl in the ternary Pt^<II> enhanced the intramolecular interaction. In both aqueous solution and crystals, the pendants took -syn -conformation which was supported by a molecular mechanics calculation. Intramolecular hydrophobic interaction of these complexes were weakened by addition of nonpolar solvents or protein denaturants such as urea.
2. The oxidation of [Fe^<II>(CN)_4(Been)] with H_2O_2 yielded consecutively the monoimine and the diimine complexes. This was due to the enhanced reactivity at the secondary amine. The monoimine complex was isolated for the first time from the diamine complex by using this dehydrogenation.
3. Intramolecular interaction between aromatic rings in Pt^<II> complexes of bpy and N-omega-phenyl-alkylethylenediamine with variation of the number of methylene brige(n) 1 to 5, was most strengthened with n=1. The intermolecular interaction between these complexes and aromatic sulfonate was most strengthened with n=3.

Report

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

    (8 results)

All Other

All Publications (8 results)

  • [Publications] Reiko Saito: "Diastereoisomers of Platinum(II)Complexes with Chiral N-Substituted 1,2-Diamines.I.Structure and Isomerization of Dichloro{(R)-2-[(2-methyl-2-aminopropyl)amino]-1-butanol}platinum(II)" Bull.Chem.Soc.Jpn.65. 1428-1437 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Reiko Saito: "Diastereoisomers of Platinum(II)Complexes with Chiral N-Substituted 1,2-Diamines.II.Structure and Dichloro[(S)-1-(2-amino-2-methylpropyl)amino-2-butanol]platinum(II)" Bull.Chem.Soc.Jpn.65. 2118-2126 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Reiko Saito, Masafumi Goto, Junzo Hirose, and Yoshinori Kidani: "Diasteromers of Platinum(II) complexes with Chiral N-Substituted 1,2-Diamines. I.Structure and Isomerization of Dichloro {(R)-2-[(2-methyl-2-aminopropyl)amino]-1-butanol} plathnum(II)" Bull.Chem.Soc.Jpn.65(5). 1428-1437 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Reiko Saito, Masafumi Goto, Junzo Hirose, and Yoshinori Kidani: "Diasteromers of Platinum(II) complexes with Chiral N-Substituted 1,2-Diamines. II.Structure of Dichloro [(S)-1-[(2-amino-2-methyopropyl)amino-2-propanol] plathnum(II)" Bull.Chem.Soc.Jpn.65(8). 2118-2126 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Reiko Saito: "Diasteromers of Platinum(II)complexes with Chiral N-Substituted 1,2-Diamines.I.Structure and Isomerization of Dichloro{(R)-2-[(2-methyl-2-aminopropyl)amino]-1-butanol} platinum(II)" Bull.Chem.Soc.Jpn.,. 65. 1428-1437 (1992)

    • Related Report
      1993 Annual Research Report
  • [Publications] Reiko Saito: "Diasteromers of Platinum(II)complexes with Chiral N-Substituted 1,2-Dimines.II.Structure of Dichloro[(S)-1-(2-amino-2-methylpropyl)amino-2-propanol] platinum(II)" Bull.Chem.Soc.Jpn.,. 65. 2118-2126 (1992)

    • Related Report
      1993 Annual Research Report
  • [Publications] Masafumi Goto: "Diastereoisomers of Platinum(II) Compleres with Chirol N-Subustituted 1,2-Diamines.I.Structure and Isomerization of Dichloroi(R)-2-[methy1-2-aminopropyl)amino]-1-butanoly platinum(II)" Bull.Chem.Soc.Jpn.65. 1428-1437 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Masafumi Goto: "Diasterecistmers of Platinum(II) Compleces with Chiral N-Subustitubed 1,2-Diamines II.Structures of Dichloro [(S)-1-(2-amino-2-methyl prophyl)amino-2-propanol]Platinum(II)" Bull.Chem.Soc.Jpn.65. 2118-2126 (1992)

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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