Synthesis and Magnetic Properties of Oligonuclear Metal Complexes

寡核金属配合物的合成及磁性

• 批准号: 08404046
• 负责人: MIKURIYA Masahiro
• 金额: $ 18.69万
• 依托单位: Kwansei Gakuin University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08404046/
• 关键词: trinuclear complexes; tetranuclear complexes; hexanuclear complexes; octanuclear complexes; oligonuclear complexes; magnetic properties; chain complexes; multidentate ligands; 結晶構造; 金属錯体; 二核金属錯体; 三核金属錯体; 四核金属錯体; 六核金属錯体; 単核錯体

Aiming at developing new oligonuclear metal complexes, some multidentate, macrocyclic, and carboxylato ligands were utilized for producing such compounds. Linear and cyclic trinuclear metal complexes as well as chain complexes were synthesized by the use of four kinds of thiolic ligands having NNS-donor sets.Heterometal trinuclear complexes were also isolated. A new NNSS-donor thiolic ligand was synthsized to give adamantane-like tetranuclear complexes. Tetranuclear, pentanuclear, hexanuclear, and octanuclear complexes were synthesized by reaction of pentadentate ligands with various metal salts. Magnetic properties of these complexes are antiferromagnetic. Macrocyclic ligands afforded dinuclear and tetranuclear complexes. Metal carboxylate dimers were examined as building blocks for oligonuclear or polynuclear formation. In most cases, chain complexes were formed. A microporous structure was found in chain complex of copper(II) benzoate. Treatment of copper(II) carboxylates led to tetranuclear and hexanuclear complexes with alternating mu-carboxylato- and mu-alkoxo-bridges.

为了开发新的寡金属配合物，利用多齿、大环和羧基配体合成了这类化合物。利用四种含NNS-给体的硫醇配体合成了线型和环状三核金属配合物以及链状配合物，并分离出了杂金属三核配合物。合成了一个新的NNSS-硫代配体，得到类金刚烷四核配合物。通过五齿配体与各种金属盐的反应，合成了四核、五核、六核和八核配合物。这些配合物的磁性是反铁磁性的。大环配体得到双核和四核配合物。金属羧酸盐二聚体作为低聚物或多核形成的结构单元进行了研究。在大多数情况下，形成链复合物。在苯甲酸铜链状配合物中发现了微孔结构。铜（II）羧酸盐的治疗导致四核和六核配合物与交替μ-carboxylato-和μ-alkoxo-桥。

项目成果

御厨正博: "Mixed-valence Hexanuclear Cobalt(II,III)Complex Made Up of Two Defective Cubane Cores" Chemistry Letters. 1998. 421-422 (1998)

Masahiro Mikuriya：“由两个有缺陷的古巴烷核心组成的混合价六核钴（II，III）络合物”化学快报1998。421-422（1998）

M.Handa, T.Nakao, M.Mikuriya, T.Kotera, R.Nukada, and K.Kasuga: "Chain Complexes of Rhodium (II) Pivalate Dimers Formed by Ligation of C=C Double Bonds and Carbonyl Oxygen of p-Quinone [{Rh_2(O_2CCMe_3)_4(p-Q)_2}{Rh_2(O_2CCMe_3)_4 }]_<eta'> P-Q=1,4-Benzoq

M.Handa、T.Nakao、M.Mikuriya、T.Kotera、R.Nukada 和 K.Kasuga：“通过 C=C 双键和 p- 的羰基氧连接形成的铑 (II) 新戊酸二聚体链络合物

T.Tanase, T.Inagaki, Y.Yamada, M.Kato, E.Ota, M.Yamazaki, M.Sato, W.Mori, K.Yamaguchi, M.Mikuriya, M.Takahashi, M.Takeda, I.Kinoshita, and S.Yano: "Tetranuclear iron (III) complexes with amino acids involving a planar (mu-oxo) (mu-hydroxo) bis (mu-alkoxo)

T.Tanase、T.Inagaki、Y.Yamada、M.Kato、E.Ota、M.Yamazaki、M.Sato、W.Mori、K.Yamaguchi、M.Mikuriya、M.Takahashi、M.Takeda、I.

M.Mikuriya and T.Kotera: "Novel Thiolato-Bridged Tetranuclear Manganese (II) and Iron (II) Complexes with Adamantane-like Cores" Chem.Lett.971-972 (1998)

M.Mikuriya 和 T.Kotera：“新型硫奥拉桥四核锰 (II) 和铁 (II) 配合物与金刚烷类核” Chem.Lett.971-972 (1998)

M.Mikuriya, H.Azuma, R.Nukada, and M.Handa: "Synthesis, X-Ray Structures, and Magnetic Properties of [Cu_2(piv)_4(Et_3N)_2] and [Cu_6(piv)_6(EtO)_6] (Hpiv=Pivalic Acid) : Role of Base for Dinuclear Adduct and Oligonuclear Formation" Chem.Lett.57-58 (1999)

M.Mikuriya、H.Azuma、R.Nukada 和 M.Handa：“[Cu_2(piv)_4(Et_3N)_2] 和 [Cu_6(piv)_6(EtO) 的合成、X 射线结构和磁性”