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Structural Conversion of Sulfur-Bridged Polynuclear Complexes by Metal Replacement Reaction

Structural Conversion of Sulfur-Bridged Polynuclear Complexes by Metal Replacement Reaction
金属置换反应硫桥多核配合物的结构转化
批准号:
07640736
负责人:
KONNO Takumi
金额:
$1.41万
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
项目状态:
已结题
起止时间:
1995 至 1996

项目摘要

项目成果

KONNO Takumi的其他基金

相关文献

中文摘要
翻译
单核钴(III)配合物中的S原子与其他金属离子结合形成S桥联的多核配合物。事实上,含有[Co(Aet)(En)_2]^<2>或fac(S)-[Co(Aet)_3]单元的S桥联多核配合物(aet=2-氨基乙硫酸酯,en=乙二胺)的化学研究已经取得了相当大的进展。另一方面,由于作为起始单核配合物的[Co(Aet)_2(En)]^的制备难度较大,所以对含有[Co(Aet)_2(En)]^单元的S桥联多核配合物的研究还很少。我们最近发现,[Ni(Aet)_2]与[CoCl2(En)_2]^反应生成了一个S桥联的CO^<III>Ni^<II>Co^<III>[Ni{Co(Aet)_2(En)}_2]^<4>(1),其中中心的Ni^<原子由两个C_2-顺(S)-[Co(Aet)_2(En)]^单元的四个配位单元配位。为了更好地理解由八面体…组成的S桥联多核配合物的化学随着[Co(Aet)_2(En)][Co(Aet)_2(En)]和[Co(Aet)_2(En)]^单元的引入,进一步研究[Co(Aet)_2(En)]和[Co(Aet)_2(En)}]Cl4中的Ni^<lt;II和gt;但反应产物不是相应的S桥联Co^<III>Cd^<II>Co^<III>三核配合物[Cd{Co(Aet)_2(En)_2(En)_2]^<4>,而是一个中性的双核配合物[Cd_3{Co(Aet)_2(En)}](2),其中Cd原子处于三角-双锥环境中。当2在水中与大量的NaNO_3反应时,生成阳离子Co^<III>_4Cd^<II>_2六核配合物[Cd_2Cl{Co(Aet)_2(En)}_4]^<7>(3)。在3中,每个Cd^<II>原子也采用三角-双锥构型,除了两个C_2-顺(S)-[Co(Aet)_2(En)]^单元中的四个S原子外,还有一个桥联的氯原子配位。用水中大量的NaNO_3处理来去除3中的桥式氯原子的尝试失败了。因此,可以合理地假设由C_2-cis(S)-[Co(Aet)_2(En)]^单元组成的Co^<III>Cd^<II>多核结构是由于Cd(II)择优为三方双锥构型而稳定的。C_2-cis(S)-[Co(Aet)_2(En)]金属配位所限制的大的共价半径和较小的Cd-Cd-S咬合角似乎是造成这种几何择优的原因。较少
英文摘要
Coordinated thiolato S atoms in mononuclear Co (III) complexes have been recognized to bind with other metal ions to form S-bridged polynuclear complexes. In fact, considerable progress has been made in the chemistry of S-bridged polynuclear complexes containing [Co (aet) (en) _2] ^<2+> or fac (S) - [Co (aet) _3] units (aet=2-aminoethanethiolate, en=ethylenediamine). On the other hand, no S-bridged polynuclear complexes containing [Co (aet) _2 (en)] ^+ units have long been studied, because of the difficulty in preparation of [Co (aet) _2 (en)] ^+ used as a starting mononuclear complex. We have recently found that the facile reaction of [Ni (aet) _2] with [CoCl_2 (en) _2] ^+ gives an S-bridged CO^<III>Ni^<II>Co^<III> trinuclear complex, [Ni {Co (aet) _2 (en)} _2] ^<4+> (1), in which the central Ni^<II> atom is coordinated by four Satoms from two C_2-cis (S) - [Co (aet) _2 (en)] ^+ units. In order to better understand the chemistry of S-bridged polynuclear complexes composed of octahedra … More l thiolato units, it is desirable to investigate other S-bridged polynuclear complexes composed of [Co (aet) _2 (en)] ^+ units.In the present study, it was found that the replacement of the Ni^<II> atom in [Ni {Co (aet) _2 (en)} _2] Cl_4 is achieved by the reaction with excess CdCl_2 in water. However, the reaction product was not a corresponding S-bridged Co^<III>Cd^<II>Co^<III> trinuclear complex [Cd {Co (aet) _2 (en)} _2] ^<4+>, but a neutral dinuclear complex [CdCl_3 {Co (aet) _2 (en)}] (2), in which the Cd atom is situated in a trigonal-bipyramidal environment. When 2 was treated with a large amount of NaNO_3 in water, a cationic Co^<III>_4Cd^<II>_2 hexanuclear complex [Cd_2Cl {Co (aet) _2 (en)} _4] ^<7+> (3) was produced. In 3 each Cd^<II> atom also adopts a trigonal-bipyramidal geometry, coordinated by a bridging Cl atom besides four S atoms from the two C_2-cis (S)- [Co (aet) _2 (en)] ^+ units. Attempts to remove the bridging Cl atom from 3 by treating with a large amount of NaNO_3 in water were unsuccessful. Accordingly, it is reasonable to assume that the Co^<III>Cd^<II> polynuclear structures composed of C_2-cis (S) - [Co (aet) _2 (en)] ^+ units are stabilized by the preference of Cd (II) for the trigonal-bipyramidal geometry. The large covalent radius of the Cd^<II> atom and the small S-Cd-S bite angle restricted by the C_2-cis (S) - [Co (aet) _2 (en)] ^+ metalloligand seem to be responsible for this geometrical preference. Less
期刊论文(9)
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会议论文
今野、佐々木、岡本: "Novel Aggregation of fac(S)-[Rh(aet)_3]by Square-Planar Palladium(II)" Chemistry Letters. 977-978 (1996)
Konno、Sasaki、Okamoto:“方形平面钯 (II) 的 fac(S)-[Rh(aet)_3] 的新颖聚合”化学快报 977-978 (1996)。
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今野、佐々木、岡本: "Novel Aggregation of fac(S)-[Rh(aet)_3] by Square-Planar Palladium(II)" Chemistry Letters. 977-978 (1996)
Konno、Sasaki、Okamoto:“方形平面钯 (II) 的 fac(S)-[Rh(aet)_3] 的新颖聚合”化学快报 977-978 (1996)。
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今野、岡本: "Synthesis, Structural Characterization, and Interconversion of S-Bridged Dinuclear and Hexanuclear Complexes Composed of cis(S)-[Co(aet)_2(en)]^+" Chemistry Letters. 975-976 (1996)
Konno,Okamoto:“由 cis(S)-[Co(aet)_2(en)]^+ 组成的 S 桥双核和六核配合物的合成、结构表征和相互转换”化学快报 975-976 (1996)。
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9
    Creation of Telescopic-type Sponge Crystal via Nano-supramolecular Chemistry
    • 批准号:
      16K13609
    • 项目类别:
      Grant-in-Aid for Challenging Exploratory Research
    • 资助金额:
      $2.33万
    • 财政年份:
      2016
    • 负责人:
      KONNO Takumi
    • 依托单位:
    Strucural Conversion of Sulfur-Bridged Polynuclear Complexes by Metal Replacement Reaction
    • 批准号:
      09640658
    • 项目类别:
      Grant-in-Aid for Scientific Research (C)
    • 资助金额:
      $2.05万
    • 财政年份:
      1997
    • 负责人:
      KONNO Takumi
    • 依托单位: