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Synthesis and Regulation of Multinueclear Metal Active Center inside the Cage-type Ligand Molecule

笼型配体分子内多核金属活性中心的合成与调控

基本信息

批准号：
18550053
负责人：
FUNAHASHI Yasuhiro
金额：
$ 2.64万
依托单位：
Nagoya Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18550053/
关键词：
Caee-type ligand Trinuclear metal complex in the cage Model of multicooper enzymes Capturing guest molecules Model of O_2-volving center CO_2-fixation かご状分子ケージ型三核銅錯体多核マンガン錯体三核パラジウム錯体

项目摘要

In them studies, we worked on rational synthesis of stable multinuclear transition metal clusters in cage-type ligand (L) for development of new active metal sites of artificial enzyme molecules, processing reactions without their decomposition. At fast, we succeeded in synthesizing a tricopper complex with a motif of the four-election O_2-reduction site in multicopper enzymes such as Laccase. Under Ar atmosphere, [Cu^<II>_3L(OH)_2(H_2O)](ClO_4)_4 (1) was made as the aqua-and dihydroxo-binding tricopper (II) species, which can catpture various anions. 1 also reacted with atmospheric carbon dioxide to give [Cu^<II>_3L(OH)_2(H_2O)](ClO_4)_4, (2), immediately. Furthermore, the cage-type ligand, L, can be applied to other transition metal ions, and we succeeded in synthesizing the cluster-type transition metal complexes of manganese(II), tripalladium(II), and cobalt(II) ions. In the trimanganese complex, [Mn_3(L)(CO_3)(OCOCH_3)(CH_3OH)_3(ClO_4)] (ClO_4) (3) , it is considered that the carbonate anion was formed from carbon dioxygen reacted with the precursor, aqua-and dihydroxo-binding trimmganese(II) center, which may be one of the best candidates for an artificial oxygen-evolving complex. In addition, we succeeded in constructing tripalladium complex (5), having the almost same structure as that of tricopper complex 2, taking carbon dioxide inside the tripalladium core of 5. In 5, the guest molecule non-covalently interacted with the cage-type ligand inside. Even in ram of a tricobalt(II) complex, similar capturing behavior for anions were observed. Construction of the other trinuclear complexes and further complicated metal centers were also newly approached in them studies

在这些研究中，我们致力于笼型配体（L）中稳定的多核过渡金属簇合物的合理合成，以开发人工酶分子的新活性金属位点，在不分解的情况下进行反应。我们成功地合成了一个以漆酶等多铜酶的四电子O_2还原位点为基序的三铜配合物。在Ar气氛下，合成了[Cu^_3L<II>（OH）_2（H_2O）]（ClO_4）_4（1），它是一种能捕获多种阴离子的水合和二羟基结合的三铜（II）物种。化合物1与大气中的二氧化碳反应，立即得到[Cu^<II>_3L（OH）_2（H_2O）]（ClO_4）_4，（2）。此外，笼型配体L可以应用于其他过渡金属离子，并且我们成功地合成了锰（II），三钯（II）和钴（II）离子的簇型过渡金属配合物。在三锰配合物[Mn_3（L）（CO_3）（OCOCH_3）（CH_3OH）_3（ClO_4）]（ClO_4）（3）中，碳酸根离子是由二氧化碳氧与前体水和二羟基结合的三锰（II）中心反应形成的，它可能是人工放氧配合物的最佳候选者之一。此外，我们成功地构建了三钯配合物（5），其具有与三铜配合物2几乎相同的结构，将二氧化碳置于5的三钯核心内。在5中，客体分子与内部的笼型配体发生非共价相互作用。即使在RAM的三钴（II）配合物，类似的捕获行为的阴离子观察。其他三核配合物的构建以及更复杂的金属中心也是新的研究方向