Stereochemical Controle for Functonal Metal Complexes

功能金属配合物的立体化学控制

• 批准号: 04303005
• 负责人: OKAWA Hisashi
• 金额: $ 5.25万
• 依托单位: KYUSYU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Co-operative Research (A)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-04303005/
• 关键词: O_2 Adduct; Ferromagnet; CO_2 Reduction; Metal Porpyrine; Chromotropism; Prototropy; Carcogenide; Supramolecule; 構造精密制御; 白金クラスター; 強磁性体; 超電導ガラス; 多電子移動; 酸素錯体; 水素結合; タングステン酸化環元酵素; 抗腫瘍性白金錯体; 伝導性錯体; スイッチング機能; ヘムエリトリン; カルコゲニド錯体; 複合系錯体

1. Stereochemical Controle of Mononuclear Complexes : Prof.Ueyama studied the redox potential controle of thiolato-Mo complexes as Mo-enzyme models by means of intramolecular hydrogen bonds. Prof.Kaizaki studied geometrical isomerization of dinuclear Cr(III) complexes, controled by intramolecular hydrogen bond. Prof.Tanaka realized the deduction of CO_2 using ruthenium(II) complexes. Prof.Kimura reported a Ni(II)-O_2 complex of a designed macrocycle. Prof.Sasaki found a reversible Mo(IV)-O_2 carrier of porpyrine ligand.2. Stereochemical Controle of Oligomeric Complexes : Prof.Uehara prepared stable O_2-adducts of dinuclear Fe(II) and Cu(I) complexes of designed dinucleating ligands. Prof.Nishida studied activation of molecular dioxygen by means of dinuclear Fe(II) complexes. Prof.Haga realized a redox-switching system based on prototropy of dinuclear benzimidazolato Ru complexes. Prof.Fukuda found a chromotropism based on dinuclear Ni(II) complexes. Prof.Yano studied hemegythrine analogs of Ru(II) ion. Prof.Ogino reported new silylene-bridged Fe complexes and their photo-induced isomerization.3. Stereochemical Controle of Complex Clusters and Complex Assemblies : Prof.Ito prepared metal-complex assemblies composed of a mu-oxo-hexa(carboxylato)M_3 and metal-porpyrines. Prof.Tatsumi found a new synthetic way for carcogenido-Ta clusters based on a trinuclear Ta complex. Prof.Ohtaki studied superionic conducting glasses of the system such as AgI-Ag_2O-CrO_3. Prof.Okawa reported 3-dimensional bimetallic assemblies exhibiting spontaneous magnetization. Prof.Munakata studied supramolecular assemblies of metal complexes of a graphite-like network.

1. 单核配合物的立体化学控制：Ueyama教授研究了硫醇-Mo配合物作为Mo酶模型通过分子内氢键的氧化还原电位控制。 Kaizaki教授研究了由分子内氢键控制的双核Cr(III)络合物的几何异构化。 Tanaka教授利用钌(II)配合物实现了CO_2的推导。 Kimura教授报道了设计的大环Ni(II)-O_2配合物。 Sasaki教授发现了可逆的卟啉配体Mo(IV)-O_2载体。 2．寡聚配合物的立体化学控制：Uehara教授制备了设计的双核配体的稳定的双核Fe(II)和Cu(I)配合物的O_2-加合物。 Nishida教授研究了通过双核Fe(II)配合物活化分子双氧。 Haga教授实现了基于双核苯并咪唑钌配合物的质子性的氧化还原开关系统。 Fukuda教授发现了基于双核Ni(II)配合物的显色性。 Yano教授研究了Ru(II)离子的血红蛋白类似物。 Ogino教授报道了新型亚硅基桥联Fe配合物及其光诱导异构化。 3．复杂簇和复杂组装体的立体化学控制：Ito教授制备了由mu-oxo-hexa(carboxylato)M_3和金属卟啉组成的金属配合物组装体。 Tatsumi教授发现了一种基于三核Ta配合物的致癌物Ta团簇的新合成方法。 Ohtaki教授研究了AgI-Ag_2O-CrO_3等体系的超离子导电玻璃。 Okawa 教授报道了表现出自发磁化的 3 维双金属组件。 Munakata 教授研究了类石墨网络金属配合物的超分子组装体。

项目成果

Megumu MUNAKATA: "Synthesis,Structures and Formation Constants of Cu(I)Complexes with Alkynes and 1,10-Phenanthroline" J.Chem.Soc.Dalton Trans.1992. 2225-2230 (1992)

Megumu MUNAKATA：“炔烃和 1,10-菲咯啉的 Cu(I) 配合物的合成、结构和形成常数”J.Chem.Soc.Dalton Trans.1992。

Hiroshi SAKIYAMA: "Macrocyclic Tetranuclear Manganese(II)Complexes of a New Dimer-of-dimers Type.Synthesis,Structure and Magnetism" J.Chem.Soc.Dalton Trans.1993. 2329-2334 (1993)

Hiroshi SAKIYAMA：“新型二聚体的二聚体类型的大环四核锰 (II) 配合物。合成、结构和磁性”J.Chem.Soc.Dalton Trans.1993。

M.Mitsumi, H.Okawa, H.Sakiyama, M.Ohba, N.Matsumoto, T.Kurisaki, and H.Wakita: "The Dithiooxalato-bridged Complex [Cr(C_2O_2S_2)_3(NiL)_3](ClO_4)_3 (L=5, 5, 7, 12, 12, 14-hexamethyl-1, 4, 8, 11-tetrazacyclotetradecane) : Synthesis, Crystal Structure, and

M.Mitsumi、H.Okawa、H.Sakiyama、M.Ohba、N.Matsumoto、T.Kurisaki 和 H.Wakita：“二硫草酸桥络合物 [Cr(C_2O_2S_2)_3(NiL)_3](ClO_4)_3

D.E.Fenton: "The Emergence of Trinuclear Constellations at Metallobiosites" J.Chem.Soc.Dalton Trans.1993. 1349-1357 (1993)

D.E.Fenton：“金属生物体中三核星座的出现”J.Chem.Soc.Dalton Trans.1993。

Norikazu UEYAMA: "cis-Dioxobis(benzenedithiolato)tungsten(V) nad related Monooxotungsten(V) and-(IV) Complexes.Model of Tungsten Oxidoreductases" J.Am.Chem.Soc.114. 7310-7311 (1992)

Norikazu UEYAMA：“顺式二氧双（苯二硫醇）钨（V）以及相关的单氧钨（V）和-（IV）复合物。钨氧化还原酶模型”J.Am.Chem.Soc.114。