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: University of Tsukuba
• 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 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07640736/
• 关键词: S-Bridged Polynuclear Complex; Strcutural Conversiton; Trigonal-bipyramidal Structure; Thiolate Ligand; Cadmium (II) Ion; Cobalt (III) Complex; Molecular Aggregation; Single-Crystal X-ray Analysis; 平面性金属イオン; 異常結合; 配位子転移; 自然分晶; 絶対配置; 結晶構造

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

单核Co（III）配合物中的硫代配位原子与其他金属离子结合形成S-桥连多核配合物。事实上，含[Co（aet）（en）_2] ^<2+>或fac（S）- [Co（aet）_3]单元（aet=2-氨基乙硫醇，en=乙二胺）的S-桥联多核配合物的化学研究已经取得了相当大的进展。另一方面，由于[Co（aet）_2（en）] ^+作为起始单核配合物的制备困难，长期以来没有研究过含[Co（aet）_2（en）]^+单元的S-桥联多核配合物。我们最近发现[Ni（aet）_2]与[CoCl_2（en）_2] ^+的反应生成了一个S-桥连的CO^<III>Ni^<II>Co^<III>三核配合物[Ni {Co（aet）_2（en）} _2] ^&lt;4+&gt;（1），其中中心Ni^<II>原子与来自两个C_2-cis（S）- [Co（aet）_2（en）] ^+单元的四个S原子配位。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 ...更多信息 在本研究中，发现<II>[Ni {Co（aet）_2（en）} _2] Cl_4中的Ni ~（2+）原子的置换是通过与过量CdCl_2在水中反应实现的。但反应产物不是相应的S-桥连的Co^<III>Cd^<II>Co^<III>三核配合物[Cd {Co（aet）_2（en）} _2] ^&lt;4+&gt;，而是中性的双核配合物[CdCl_3 {Co（aet）_2（en）}]（2），其中Cd原子处于三角-双锥环境。当2与大量的NaNO_3在水中反应时，生成阳离子型Co <III>^4Cd ^<II>2六核配合物[Cd_2Cl {Co（aet）_2（en）} _4] ^&lt;7+&gt;（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-cis（S）- [Co（aet）_2（en）] ^+单元中的四个S原子外，还与一个桥连Cl原子配位。用大量的NaNO_3水溶液处理3，除去桥连的Cl原子，但没有成功。因此，我们有理由认为，<III><II>由C_2-cis（S）- [Co（aet）_2（en）] ^+单元组成的Co^ Cd^多核结构是由于Cd（II）对三角双锥几何构型的偏好而稳定的。Cd ~（2+）原子的大共价半径<II>和C_2-cis（S）- [Co（aet）_2（en）]~（2+）金属配体限制的小S-Cd-S咬合角可能是导致这种几何偏好的原因。少

项目成果

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)。

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)。

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)。

T.Konno and K.Okamoto: "Stoichiometric Interconversion of S-Bridged Rh^<III>_2Ag^I_3 Pentanuclear and Rh^<III>_4Ag^I_5 Nonanuclear Structure : Synthesis and Structural Characterization of [Ag_3 {Rh (aet) _3} _2] ^<3+> and [Ag_5 {Rh (aet) _3} _4 ] ^<5+> (a

T.Konno 和 K.Okamoto：“S-桥接 Rh^<III>_2Ag^I_3 五核和 Rh^<III>_4Ag^I_5 非核结构的化学计量互换：[Ag_3 {Rh (aet) _3} 的合成和结构表征”

今野、岡本: "Stoichiometric Interconversion of S-Bridged Rh^<III>_2Ag^I_3 Pentanuclear and Rh^<III>_4Ag^I_5 Nonanuclear Structure" Inorganic Chemistry. 37. (1997)

Konno，Okamoto：“S-桥接 Rh^<III>_2Ag^I_3 五核和 Rh^<III>_4Ag^I_5 非核结构的化学计量互变”无机化学 37。（1997）