Design and development of new cyano-bridged metal complexes and syntheses of its rotaxane

新型氰基桥金属配合物的设计开发及其轮烷的合成

基本信息

  • 批准号:
    07640741
  • 负责人:
  • 金额:
    $ 1.47万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
  • 财政年份:
    1995
  • 资助国家:
    日本
  • 起止时间:
    1995 至 1997
  • 项目状态:
    已结题

项目摘要

(1) Mixed copper (II) chelates of the type [Cu (trop/hino) (diamine)] ClO_4 were prepared with a tropolonato or hinokitiolato ligand (trop/hino) and N,N-dimethyl, N,N'-dimethyl, N,N,N'-trimethyl or N,N,N', N'-tetramethyl-ethylenediamine. These chelates were generally similar to the corresponding beta-diketonato chelates, in particular with respect to their characteristic solvatochromism, i.e., the shifts of their d-d bands to the red with increasing DN (donor number) of the solvent.(2) Eleven mixed-ligand chelates of Ni (II) containing a molecule of N,N-di-, N,N,N'-tri-, or N,N,N', N'-tetramethyl-ethylenediamine, and a tropolone (trop) or hinokitiolate (hino) ligand, were prepared, and their electronic spectra in solid state and in various organic solvents were studied. Most systems studied were green, containing octahedral chelate species [Ni (trop/hino) (diamine) (H_2O/Solvent)_2]^+ or [Ni (NO_3) (trop/hino) (diamine)], but some were red, containing square planar [Ni (trop/hino) (dia … More mine)]^+, an equilibrium between the octahedral and square planar species was sometimes observed in solutions. Strong spectral resemblances with the corresponding diamine-beta-diketonate chelates of Ni (II) were observed.(3) The solid-phase thermal reactions of trans-diaquabis (diamine) nickel (II) complexes (trans- [Ni (diamine)_2 (H_2O)_2] X_2) were investigated by means of TG/DTA and DSC,and high-temperature electronic spectrometry, where the diamine is an optically active diamine such as (1S,2S) -1,2-diphenyl-1,2-ethanediamine, (1R,2R) -1,2-cyclo-hexanediamine, or (S) -4-methyl-1,2-pentanediamine, and X is Cl^-, Br^-, or NO_3^-. Several complexes were peculiarly transformed into cis- [NiX_2 (diamine)_2] upon thermal deaquation-anation, and then isomerized to trans- [NiX_2(dimaine)_2] upon further heating. The results were in contrast to the reactions of the complexes with the coresponding racemic diamines which underwent a simple deaquation-anation, retaining an original trans configuration. The differences must come from a slight difference in the conformation of diamine ligands between trans- [Ni (R-diamine) (S-diamine) (H_2O)_2]X_2 which is obtained for the rac-diamines and trans- [Ni (R- or S-diamine)_2 (H_2O)_2]X_2 which is obtained for the optically active diamines. Less
(1)以三甲氧基铜和N,N-二甲基,N,N‘-二甲基二甲基,N,N,N’-三甲基或N,N,N‘,N’-四甲基乙二胺为配体合成了[Cu(trop/Hino)(二胺)]ClO_4混合铜(II)络合物。合成了11种含N,N-二,N,N,N‘-三-或N,N,N’-四甲基乙二胺和三聚体(TROP)或HINO(HINO)配体的N,N-二,N,N,N‘-三-或N,N,N’,N‘-四甲基乙二胺的镍(II)混合配体。所研究的大多数体系是绿色的,含有八面体螯合物种[Ni(trop/hiino)(二胺)(H_2O/溶剂)_2]^+或[Ni(NO_3)(trop/hiino)(二胺)],但也有一些是红色的,含有方形平面[Ni(trop/hiino)(dia…更多的矿物质)]^+,有时在溶液中观察到八面体和正方形平面物种之间的平衡。(3)用TG/DTA、DSC和高温电子能谱研究了反式二水双(二胺)镍(II)配合物(反式[Ni(二胺)_2(H_2O)_2]X_2)的固相热反应,其中二胺是光学活性的二胺,如(1S,2S)-1,2-二苯基-1,2-乙二胺,(1R,2R)-1,2-环己二胺,或(S)-4-甲基-1,2-戊二胺,X为氯^-、溴^-或硝酸^-。几种配合物在热脱水阳极时特殊地转变为顺式-[NiX_2(二胺)_2],然后在进一步加热时异构化为反式-[NiX_2(二胺)_2]。这一结果与配合物与相应的外消旋二胺的反应相反,后者经历了简单的脱水-脱水反应,保留了原始的反式构型。这种差异可能源于反式[Ni(R-或S-二胺)(S-二胺)(H_2O)_2]X_2和反式[Ni(R-或S-二胺)_2(H_2O)_2]X_2在构象上的细微差别。较少

项目成果

期刊论文数量(15)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
井原良訓: "Solnatochromic mixed-ligand copper(II)chelates with N- or N,N^<>-methylated ethylenediamines and tropolonato or hinokitiolato ligands" Polyhedron. (1996)
Yoshinori Ihara:“Solnatochromic 混合配体铜 (II) 与 N- 或 N,N,N-甲基化乙二胺和 troponato 或 hinokitiolato 配体螯合” Polyhedron (1996)。
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井原 良訓: "Preparation and Spectral Study of Mixed-ligand Nickel(II) Chelates Containing N- or N,N'-Methylated Ethylenediamines and Tropolonate or Hinokitiolate Ligands" Polyhedron. (in press). (1998)
Yoshinori Ihara:“含有 N- 或 N,N-甲基化乙二胺和托泊酸或扁柏酸配体的混合配体镍 (II) 螯合物的制备和光谱研究”(出版中)。
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Y.Ihara and R.Nakamura: "Solid-phase thermal cis-to-trans isomerization of the mickel (II) complexes containing 1-benzyl-1,2-ethanediamine" Thermochim.Acta. 302. 211-214 (1997)
Y.Ihara 和 R.Nakamura:“含有 1-苄基-1,2-乙二胺的米克尔 (II) 配合物的固相热顺式至反式异构化”Thermochim.Acta。
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井原 良訓: "Solvatochromic Mixed-ligand Copper(II)Chelates with N-or N,N'-Methylated Ethylenediamines and Tropolonato or Hinokitiolato Ligands" Polyhedron. 15. 3643-3646 (1996)
Yoshinori Ihara:“溶剂变色混合配体铜 (II) 与 N-或 N,N-甲基化乙二胺和 Tropolonato 或 Hinokitiolato 配体的螯合物”Polyhedron 15. 3643-3646 (1996)。
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    0
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井原 良訓: "Solid-phase Thermal Cis-to-trans Isomerization of the Nickel (II) Complexes Containing 1-Benzyl-1,2-ethanediamine" Thermochim.Acta. 302. 211-214 (1997)
Yoshinori Ihara:“含 1-苄基-1,2-乙二胺的镍 (II) 配合物的固相热顺反式异构化”Thermochim.Acta. 302. 211-214 (1997)
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IHARA Yoshinori其他文献

IHARA Yoshinori的其他文献

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{{ truncateString('IHARA Yoshinori', 18)}}的其他基金

Development of thermochromic teaching materials at which the temperature that the color change takes place can be controlled arbitrarily and which teachers and pupils can readily prepare
开发可任意控制变色温度、师生可轻松制作的热致变色教材
  • 批准号:
    24501047
  • 财政年份:
    2012
  • 资助金额:
    $ 1.47万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
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