Research of Molecular Design, Reactivity, and Some Properties for s- and Se-Bridged Polynuclear Complexes

s-和 Se-桥多核配合物的分子设计、反应性和一些性质的研究

基本信息

  • 批准号:
    02640467
  • 负责人:
  • 金额:
    $ 1.28万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for General Scientific Research (C)
  • 财政年份:
    1990
  • 资助国家:
    日本
  • 起止时间:
    1990 至 1991
  • 项目状态:
    已结题

项目摘要

In this work, we obtained the following results(1)-(3):(1)Three kinds of S-bridged dinuclear complexes, DELTA- and LAMBDA-[CO_2(aet)_3(dien)]^<3+>(aet=2-aminoethanethiolate and dien = diethylenetriamine), DELTA- and LAMBDA-[Co_2(aet)_3(dpt)]^<3+> (dpt = bis(3-aminopropyl)amine)), and DELTA_<LLL>-[CO_2(L-cys-N,S)_3(dien)]^<3+> (L-cys = L-cysteinate), were prepared by the reaction of [Co(aet)_3] or DELTA_<LLL>-[CO(L-cys-N,S)_3]^<3-> with [CoCl_3(dien)] or [CoCl_3(dpt). The isomers were characterized from their absorption, CD, and ^<13>CNMR spectra.(2)The novel mononuclear, dinuclear, and trinuclear cobalt(III) complexes with D-penicillaminate (D-pen), LAMBDA_<DDD>-fac(S)-[Co(D-(pen-N,S)_3]^<3->, LAMBDA_<DDD>-[Co(Co(D-pen-N,S)_3(dien)], LAMDA_<DDD>-[Co{Co(D-pen-N,S)_3(D-pen-N,O,S)]^<2->, and LAMBDA_<DDD>DELTA_<DDD>-[Co{Co(D-pen-N,S)_3}_2]^<3-> were prepared. These complexes were characterized from their electronic absorption, CD, and ^<13>C NMR spectra. These complexes formed selectively … More each one isomer. The stereoselectivity for the D-pen complexes is discussed in comparison with that of the corresponding L-cys ones. the D-pen polynuclear complexes exhibited characteristic absorption spectral behaviors in the visible region. The ^<13>C NMR spectral behaviors for the D-pen complexes are connected with those of the corresponding L-cys ones.(3) The novel T-cage-type Se-bridged polynuclear complexes with 2-aminoethaneselenolate (aese) [{Co(aese)_3}_4Zn_mX]^<n+> (X = O (m,n=4,6) or C1 (m,n=3,5 and 4,7)) and [{Rh(aese)_3}^4Zn_4O]Br_6, have been synthesized. Of these complexes, the spontaneous resolution was recognized for the Co(III) and Rh(III) complexes with the [Zn_4O]^<6+> core. The crystal structure of was determined by the X-ray diffraction method. The four octahedral fac(Se)-[Co(aese)_3] subunits are bound to the tetrahedral [Zn_4O]^<6+> core with the central mu^4-oxygen atom to take to kate a tetrahedral arrangement, giving T symmetrical structure. The chiral configurations are regulated to DELTA or RAMDA for all four fac(Se)-[Co(aele)_3] subunits. The electronic absorption and CD spectral behavior of these complexes are discussed in comparison with those of related mononuclear and linear-type S -bridged trinuclear complexes, and the corresponding cage-type polynuclear complexes. Less
在这项工作中,我们得到了以下结果(1)-(3):(1)三种硫桥双核配合物DELTA-和LAMBDA-[CO_2(aet)_3(dien)]^&lt;3+&gt;(aet=2-氨基乙硫醇盐和dien =二亚乙基三胺),DELTA-和LAMBDA-[Co_2(aet)_3(dpt)]^&lt;3+&gt;(dpt =双(3-氨基丙基)胺))和DELTA_<LLL>-[CO_2(L-cys-N,S)_3(dien)]^&lt;3+&gt;(L-cys = L-半胱氨酸),通过[Co(aet)_3]或DELTA_<LLL>-[CO(L-cys-N,S)_3]^<3->与[CoCl_3(dien)]或[CoCl_3(dpt)。通过吸收光谱、CD光谱和13 CNMR光谱对异构体进行了表征<13>。(2)合成了新的单核、双核和三核钴(III)配合物LAMBDA_<DDD>-fac(S)-[Co(D-(pen-N,S)_3]^<3->、LAMBDA_<DDD>-[Co(D-pen-N,S)_3(dien)]、LAMDA_ -[<DDD>Co{Co(D-pen-N,S)_3(D-pen-N,O,S)]^<2->和LAMBDA_<DDD>DELTA_<DDD>-[Co{Co(D-pen-N,S)_3}_2]^<3->。通过电子吸收光谱、圆二色性光谱和~ 13 C核磁共振谱对配合物进行了表征<13>。这些复合物选择性地形成 ...更多信息 每一个异构体。与相应的L-cys配合物的立体选择性进行了比较,讨论了D-笔配合物的立体选择性。D-pen多核配合物在可见光区表现出特征吸收光谱行为。D-pen<13>配合物的~ 13 C NMR谱行为与相应的L-cys配合物的~ 13 C NMR谱行为相联系。(3)合成了2-氨基乙硒醇(aese)[{Co(aese)_3}_4Zn_mX]^&lt;n+&gt;(X = O(m,n= 4,6)或Cl(m,n= 3,5和4,7))与[{Rh(aese)_3}^4Zn_4O]Br_6的T笼型硒桥多核配合物。在这些配合物中,以[Zn_4O]^&lt;6+&gt;为核心的Co(III)和Rh(III)配合物被认为是自发拆分的。用X射线衍射法测定了配合物的晶体结构。四个八面体的fac(Se)-[Co(aese)_3]亚基与四面体的[Zn_4O]^&lt;6+&gt;核结合,形成四面体排列,形成T对称结构。四种fac(Se)-[Co(aele)_3]亚基的手性构型均被调节为DELTA或RAMDA。讨论了这些配合物的电子吸收和CD光谱行为,并与相关的单核和线型S -桥连三核配合物以及相应的笼型多核配合物进行了比较。少

项目成果

期刊论文数量(12)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
K. Okamoto, Y. Watanabe, T. Konno, and J. Hidaka: "Syntheses and Properties of T-Cage-Type Se-Bridged Polynuclear Co(III) and Rh(III) Complexes with 2-Aminoethaneselenolate (aese). Crystal Structure of [{Co(aese)_3}_4Zn_4O](ClO_4)^6" Bull.Chem.Soc.Jpn. 65
K. Okamoto、Y. Watanabe、T. Konno 和 J. Hidaka:“T 笼型 Se 桥多核 Co(III) 和 Rh(III) 与 2-氨基乙烷硒酸盐 (aese) 配合物的合成和性能。晶体
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    0
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岡本 健一: "Stereoselective Formation and Some Properties of Polynuclear Cobalt(III)Complexes with D-Penicillaminate" Bull.Chem.Soc.Jpn.,. 65. 794-798 (1992)
Kenichi Okamoto:“多核钴 (III) 与 D-青霉胺配合物的立体选择性形成和一些性质”Bull.Chem.Soc.Jpn., 65. 794-798 (1992)
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    0
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T. Konno, K. Okamoto, J. Hidaka: "Preparation and Characterization of [CO_2(bidentate-N,S)_3(triamine)]-Type S-Bridged Dinuclear Complexes" Bull.Chem.Soc.Jpn. 63. 3027-3029 (1990)
T. Konno、K. Okamoto、J. Hidaka:“[CO_2(二齿-N,S)_3(三胺)]-型 S-桥双核配合物的制备和表征”Bull.Chem.Soc.Jpn。
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    0
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K. Okamoto, T. Yonemura, T.Konno, and J. Hidaka: "Stereoselective Formation and Some Properties of Polynuclear Cobalt(III)Complexes with D-Penicillaminate" Bull.Chem.Soc.Jpn. 65. 794-798 (1992)
K. Okamoto、T. Yonemura、T.Konno 和 J. Hidaka:“多核钴 (III) 与 D-青霉胺配合物的立体选择性形成和一些性质” Bull.Chem.Soc.Jpn。
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  • 影响因子:
    0
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  • 通讯作者:
岡本 健一: "Preparation and Spectroscopic Properties of Cageーtype SeーBridged Polynuclear Complexes with 2ーAminoethaneselenolate(aese)." Bull.Chem.Soc.Jpn.,. (1992)
Kenichi Okamoto:“笼型 Se 桥多核配合物与 2-氨基乙烷硒酸盐 (aese) 的制备和光谱特性”,Bull.Chem.Soc.Jpn.,(1992 年)
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OKAMOTO Ken-ichi其他文献

OKAMOTO Ken-ichi的其他文献

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{{ truncateString('OKAMOTO Ken-ichi', 18)}}的其他基金

Stereoselective Formation and Chemical Properties of Chiral Polynuclear Complexes Depending on Oxidation Numbers
取决于氧化数的手性多核配合物的立体选择性形成和化学性质
  • 批准号:
    14540510
  • 财政年份:
    2002
  • 资助金额:
    $ 1.28万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Development of Polyimide Polymers membranes for Pervaporation and Vapor-Permeation of Hydrocarbon Mixtures.
用于碳氢化合物混合物渗透蒸发和蒸汽渗透的聚酰亚胺聚合物膜的开发。
  • 批准号:
    08455367
  • 财政年份:
    1996
  • 资助金额:
    $ 1.28万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
金属の結合様式に基づく硫黄架橋多核錯体の組織化と制御
基于金属结合模式的硫桥多核配合物的组织与控制
  • 批准号:
    07454172
  • 财政年份:
    1995
  • 资助金额:
    $ 1.28万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
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