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Studies on the Preparation of Dinuclear Transition Metal Complexes, and the Activation-states of Small Molecules and the Magnetic Interactions involved therein

双核过渡金属配合物的制备、小分子活化态及其磁相互作用的研究

基本信息

批准号：
62470040
负责人：
UEHARA Akira
金额：
$ 4.22万
依托单位：
Kanazawa University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1989
项目状态：
已结题

项目摘要

(1) Dinuclear Iron Complexes: dinuclear mixed-valence iron(II,III) centers have been known to be involved in the iron proteins such as semi-methemerythrin and pink uteroferrin. We designed two new dinucleating ligands, 2,6- bis[bis(2-pyridylmethyl and 2-benzimidazolylmethyl)aminomethyl]-4-methylphenol, which have bilaterally bisymmetric structures. The dinuclear iron(II,II), (II,III) and (III,III) complexes containing the above ligands and carboxylate ions were newly prepared. From the results of electronic, ESR and Mossbauer spectra, and mignbtic susceptibilities, it was found that (1) the iron(II,III) complex is much more stabilized than the iron(II,II) and (III,III) complexes; (2) the iron(II,III) complex belongs to the so-called Class II mixed-valence complex; and (3) a weak antiferromagnetic interaction it exerted between the two iron ions.(2) Dinuclear and Tetranuclear Manganese Complexes: the dinuclear and tetranuclear manganese centers in photosystem II (PS II) in green plants have been shown to play a-n essential role for the catalytic oxidation of water to molecular oxygen (2H_2O -> O_2 + 4H^+ + 4e ). We newly prepared the dinuclear manganese(II,II), (II,III), (III,IV), and (IV,IV) complexes with 2,6 bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol. and the tetranuclear manganese(II,III,III,II) complexes with tris(2-pyridylmethyl)amine (N_4-py).The structures of the complexes were clarified by means of X-ray crystallography. Among these complexes, the N_4-py complex showed the sign of possibility of the catalytic oxidation of water, but we have not yet obtained good enough evidences. The study in this category has great potentialities for future level opment.(3) We succeeded in isolating the dinuclear cobalt(II,II) complexes which bind reversibly molecular oxygen. A weak antiferromagnetic interaction was recognized in the dinuclear chromium(III,III) complexes which contain a linear cyanide ion as the bridging ligand.

(1)双核铁络合物：已知双核混合价铁（II，III）中心参与铁蛋白质如半-甲基血红蛋白和粉红子宫铁蛋白。我们设计了两个新的双核配体2，6-双[双（2-吡啶甲基和2-苯并咪唑甲基）氨甲基]-4-甲基苯酚，它们具有双对称结构。新合成了含上述配体和羧酸根离子的双核铁（II，II）、（II，III）和（III，III）配合物。电子能谱、ESR谱、穆斯堡尔谱和迁移率的结果表明：（1）铁（Ⅱ，Ⅲ）络合物比铁（Ⅱ，Ⅱ）和铁（Ⅲ，Ⅲ）络合物稳定得多;（2）铁（Ⅱ，Ⅲ）络合物属于所谓的Ⅱ类混合价络合物;（3）它在两个铁离子之间有弱的反铁磁相互作用。(2)双核和四核锰配合物：绿色植物光系统II（PS II）中的双核和四核锰中心在催化水氧化为分子氧（2H_2O -> O_2 + 4 H ^++4e）中起着重要作用。本文首次合成了2，6-二[二（2-吡啶甲基）氨甲基]-4-甲基苯酚与双核锰（II，II），（II，III），（III，IV）和（IV，IV）的配合物。三（2-吡啶甲基）胺（N_4-py）与锰（Ⅱ，Ⅲ，Ⅲ，Ⅱ）的四核配合物，用X-射线单晶衍射法确定了配合物的结构。在这些配合物中，N_4-py配合物显示出催化氧化水的可能性，但我们还没有得到足够的证据。这一领域的研究具有很大的发展潜力。(3)我们成功地分离出双核钴（II，II）配合物，可逆地结合分子氧。一个弱的反铁磁相互作用被确认在双核铬（III，III）配合物，其中包含一个线性氰离子作为桥接配体。