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

• 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

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，我们致力于在笼型配体（L）中合理合成稳定的多核过渡金属簇，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。很快，我们成功地合成了以漆酶等多铜酶中的四选O_2还原位点为基序的三铜复合物。在Ar气氛下，[Cu^<II>_3L(OH)_2(H_2O)](ClO_4)_4(1)被制备为水结合和二羟基结合的三铜(II)物种，它可以捕获各种阴离子。 1还与大气中的二氧化碳反应，立即得到[Cu 2 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，我们成功合成了锰(II)、三钯(II)和钴(II)离子的簇状过渡金属配合物。在三锰络合物[Mn_3(L)(CO_3)(OCOCH_3)(CH_3OH)_3(ClO_4)](ClO_4)(3)中，认为碳酸根阴离子是由二氧化碳与前体水反应形成的。和二羟基结合三锰（II）中心，它可能是人工放氧复合物的最佳候选者之一。此外，我们成功构建了三钯配合物（5），其结构与三铜配合物2几乎相同，将二氧化碳带入5的三钯核心内。在5中，客体分子与笼型分子发生非共价相互作用。里面的配体。即使在三钴（II）络合物的公羊中，也观察到类似的阴离子捕获行为。其他三核配合物和更复杂的金属中心的构建也在这些研究中得到了新的探讨

项目成果

Adsorption of microorganisms onto an artificial siderophore-modified Au substrate

• DOI: 10.1016/j.bios.2007.08.015
• 发表时间: 2007-12-15
• 期刊: BIOSENSORS & BIOELECTRONICS
• 影响因子: 12.6
• 作者: Inomata, Tornohiko;Eguchi, Hiroshi;Masuda, Hideki
• 通讯作者: Masuda, Hideki

Micro-columnar crystals with (-O=V-Pd-)n infinite chain structures assembled by hetero-dinuclear metal complexes

• DOI: 10.4028/www.scientific.net/amr.11-12.273
• 发表时间: 2006-01-01
• 期刊: AICAM 2005
• 作者: Funahashi, Y.;Kamimura, T.;Masuda, H.
• 通讯作者: Masuda, H.

Preparation of a carboxylate-binding mononuclear iron(II)(-)-sparteine complex with structural distortion and its reaction with oxidants

结构畸变的羧酸结合单核铁(II)(-)-金雀花配合物的制备及其与氧化剂的反应

• 发表时间: 2007
• 期刊: Chemistry Letters 36
• 作者: T. Okumura;S. Hayami;T. Ozawa;Y. Funahashi;Y. Maeda;H. Masuda
• 通讯作者: H. Masuda

Is it possible for an iron ion in an aqueous solution to see a dream of oxygenase

水溶液中的铁离子能否看到加氧酶的梦想

• 发表时间: 2006
• 期刊: Kagaku 61
• 作者: N. Ichieda;T. Kamimura;S. Yamaguchi;Y. Funahashi;T. Ozawa;K;Jitsukawa;H. Masuda;Y. Funahashi
• 通讯作者: Y. Funahashi

Syntheses, characterization, and dioxygen reactivities of Cu(I) complexes with cis, cis-I, 3, 5-triamocyclohexane dedvatives: A Cu(III)_2O_2 intemediate exhibiting higher C-H activation.

Cu(I) 与顺式、顺式-I、3, 5-三氨基环己烷衍生物配合物的合成、表征和分子氧反应性：具有较高 C-H 活化作用的 Cu(III)_2O_2 中间体。

• 发表时间: 2007
• 期刊: Inorganic Chemistry 46
• 作者: Y. Kajita;H. Arii;T. Saito;Y. Saito;S. Nagatomo;T. Kitagawa;Y. Funahashi;T. Ozawa;H. Masuda
• 通讯作者: H. Masuda