The trinuclear copper(I) thiolate complexes [Cu3(NGuaS)3](0/1+) and their dimeric variants [Cu6(NGuaS)6](1+/2+/3+) with biomimetic redox properties.
The trinuclear copper(I) thiolate complexes [Cu3(NGuaS)3](0/1+) and their dimeric variants [Cu6(NGuaS)6](1+/2+/3+) with biomimetic redox properties.
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DOI：
10.1002/anie.201008076
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发表时间：
2011-05
影响因子：
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通讯作者：
A. Neuba;U. Flörke;W. Meyer-klaucke;M. Salomone-Stagni;E. Bill;E. Bothe;Petra Höfer;G. Henkel
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文献类型：
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作者：
A. Neuba;U. Flörke;W. Meyer-klaucke;M. Salomone-Stagni;E. Bill;E. Bothe;Petra Höfer;G. Henkel
作为各种电子传递链的积极参与者，铜元素在生物学中起着核心作用。[1]这种特殊的位置可以追溯到特定的氧化还原性质起源于d9和d10铜原子对配位几何形状和配体场的需求之间的独特相互作用。在这方面，网站单核协调（例如，在天青蛋白和质体蓝蛋白）的蛋白质环境的基质效应的条件。[2]双核系统也有类似的基质效应，如存在于细胞色素c氧化酶或N2 O还原酶中的CuA，它们含有由两个硫醇供体功能桥接的铜原子。[3]在实验室中对这些生物活性铜位点进行人工重建以模拟其特征特性的方法至今未能成功，因为难以用合适的其他影响来取代天然基质效应。这个问题也适用于细胞色素c氧化酶或N2 O还原酶中的CuA模型络合物，[4]尽管在配位数和配体场方面具有相似性，但它们的氧化还原性质和中心{Cu 2S 2}菱形的拉伸程度通常与原型非常显着不同。[5]此外，还有许多其他双核硫醇盐配合物的例子，它们甚至与天然的CuA有更大的不同。[6]美国联邦调查局
As the active participant of various electron-transport chains, the element copper plays a central role in biology.[1] This privileged position can be traced back to specific redox properties originating in the unique interplay between demands of d9 and d10 copper atoms towards coordination geometries and ligand fields. In this respect, sites for mononuclear coordination (eg, in azurin and plastocyanin) are conditioned by matrix effects of the protein surroundings.[2] Similar matrix effects are experienced by dinuclear systems, such as CuA present in cytochrome-c oxidases or N2O reductases, which contain copper atoms bridged by two thiolate donor functions.[3]Artificial reconstruction of these biologically active copper sites to model their characteristic properties in the laboratory failed to date because of difficulties in replacing the natural matrix effects by suitable other influences. This problem also holds for model complexes of CuA within cytochrome-c oxidases or N2O reductases,[4] which—in spite of similarities with respect to coordination numbers and ligand fields—often differ very significantly from their archetypes in their redox properties and the degree of stretching of their central {Cu2S2} rhombus.[5] In addition, there are numerous other examples of dinuclear thiolate complexes which differ even further from the natural CuA.[6]