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

通过金属置换反应进行硫桥多核配合物的结构转化

基本信息

批准号：
09640658
负责人：
KONNO Takumi
金额：
$ 2.05万
依托单位：
GUNMA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640658/
关键词：
S-Bridged Polynuclear Complex Strcutural Conversiton Palladium(II) Ion Thiolate Ligand Silver(I) Ion Zinc(II) Ion Cobalt(III) Complex Single-Crystal X-ray Analysis らせん構造光学分割チオレート配位子分子集合体

项目摘要

The aggregation of octaetal complexes with two or three thiolate ligands assisted by metal ions has been shown to form a variety of S-bridged polynuclear complexes containing several chiral centers. It has been noted that the structures of these polynuclear complexes are highly dependent on the coordination geometry of metal ions incorporated with the octahedral complexes. In order to better understand the properties characteristic of the S-bridged structure of this type, it is necessary to investigate analogous S-bridged polynuclear complexes composed of (tris)- or (bis)thiolato complex-units.In this study, we have found that the novel S-bridged Co^<III>Ag^I_3Co^<III> pentanuclear complexes, [Ag_3{Co(aet) _3}_2] ^<3+> and [Ag_3{Co(L-cys-N,S) _3}_2, ] ^<3->, were prepared by reacting fac(S)-[Co(aet or L-cys-N,S) _3] ^<0or3-> with linear Ag^+. In the Co^<III>Ag^I_3Co^<III>structure, the two thiolato S atoms from two fac(S)-[Co(aet or L-cys-N,S) _3] ^<0or3-> units coordinate to each of three Ag atoms, such that the three S-Ag-S linkages form a triple helical structure, On the other hand, the reaction of an S-bridged Co^<III>Ni^<II>Co^<III> trinuclear complex, [Ni{Co(aet) _2 (en)}_2]Cl_4, with Na_2 [PdCI_4 ] in a ratio of 1 : 1 gave an S-bridged Co^<III>Pd^<II>Co^<III> trinuclear complex, [Pd{Co(aet) _2 (en)}_2]Cl_4, while the corresponding 1 : 2 reaction produced an S-bridged Co^<III>Pd^<II> dinuclear complex, [PdCl_2{Co(aet) _2 (en)}]CI.In the Co^<III>Pd^<II>Co^<III> structure the Pd^<II> atom is coordinated by four S atoms from two cis(S)-[Co(aet) _2 (en)] ^+ units, while the Pd_<II> atom in the Co_<III>Pd_<II> structure is coordinated by two Cl atoms besides two S atoms from one octahedral unit.

在金属离子的辅助下，具有两个或三个硫醇配体的八缩醛配合物的聚集已被证明可以形成多种含有多个手性中心的S-桥连多核配合物。已经注意到，这些多核配合物的结构高度依赖于与八面体配合物结合的金属离子的配位几何形状。为了更好地理解这类S-桥结构的性质特征，有必要研究由（三）-或（二）-硫醇基配合物单元组成的类似S-桥多核配合物，在本研究中，我们发现通过fac（S）-[Co（aet或L-cys-N，S）_3]^与线性Ag ^+反应，制备了新型S-桥Co ^Ag^I_3Co ^五核配合物[Ag_3 {Co（aet）_3}_2]^<3 +>和[Ag_3 {Co（L-cys-N，S）_3}_2，]^。<III><III><3-><0or3->在Co ^Ag ^I_3Co ^结构中，两个巯基S原子从两个面（S）-[Co（aet或L-cys-N，S）_3]~（2+）单元分别与三个Ag原子配位，使三个S-Ag-S键形成三螺旋结构。另一方面，S-桥连的Co~（2+）Ni~（2+）Co~（2+）三核配合物，[Ni {Co（aet）_2（en）}_2] Cl_4与Na_2 [PdCl_4]按1：1的比例反应，合成了一种S-桥连的Co ^Pd ^Co ^三核配合物[Pd {Co（aet）_2（en）}_2] Cl_4，而相应的1：2反应生成S-桥连的Co ^Pd ^双核配合物，[PdCl_2 {Co在Co ^Pd ^Co ^结构中，Pd ^原子被来自两个顺式（S）-[Co ^（C3）2]的四个S原子配位。（aet）_2（en）]^+配位，而Co_Pd_结构中的Pd_除了与一个八面体单元中的两个S原子配位外，还与两个Cl原子配位。<III><III><0or3-><III><II><III><III><II><III><III><II><III><II><III><II><II><III><II>