Complexes of CuII with mixed-donor phenanthroline-containing macrocycles:: analysis of their structural, redox and spectral properties in the context of Type-1 blue copper proteins biomimetic models
Complexes of CuII with mixed-donor phenanthroline-containing macrocycles:: analysis of their structural, redox and spectral properties in the context of Type-1 blue copper proteins biomimetic models
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DOI：
10.1016/j.ica.2005.01.014
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发表时间：
2005-04-15
影响因子：
2.8
通讯作者：
Yari, A
中科院分区：
文献类型：
--
作者：
Arca, M;Azimi, G;Yari, A
大环L-1-L-3分别具有N2S2O-、N2S2-和n2s3给体集，并含有1,10-菲罗啉单元，在乙氧乙酸和甲基乙酸溶液中与Cu-II相互作用，生成1:1 [M(L)]（2+）络合物。化合物[Cu(L-1)(ClO4)]ClO4 (1), [Cu(L-2)(ClO4)]ClO4中心点1/ 2h (2)O(2)和[Cu(L-3)](ClO4)(2)(3)在固体状态下被分离出来，并通过x射线衍射研究对前两个化合物进行了表征。L-1和l2在阳离子配合物中采用的构象揭示了环的脂肪族部分折叠在含有杂芳部分的平面上，配体通过施加压力将金属中心包裹在它们的腔内。分别以正方形为基础的金字塔和正方形平面几何。在这两种配合物中，金属离子通过与ClO4-配体相互作用来完成其配位球。含有1:2阳离子配合物的化合物[Cu(L-3)(2)](PF6)(2)(4)也在固态下被分离出来：EPR光谱测量表明该配合物中存在CuN4发色团。研究了1-4的EPR和电子光谱特征，并与1型蓝铜蛋白的氧化还原特性进行了比较。L-1-L-3对切盐的化学计量量的反应性也进行了测试[CuCl(PPh3)(3)], (c) 2005 Elsevier B.V.版权所有。
The macrocycles L-1-L-3 having N2S2O-, N2S2-, and N2S3-donor sets, respectively, and incorporating the 1,10-phenanthroline unit interact in EtOH and MeCN solutions with Cu-II to give 1:1 [M(L)](2+) complex species. The compounds [Cu(L-1)(ClO4)]ClO4 (1), [Cu(L-2)(ClO4)]ClO4 center dot 1/2H(2)O (2) and [Cu(L-3)](ClO4)(2) (3) were isolated at the solid state and the first two also characterised by X-ray diffraction studies. The conformation adopted by L-1 and L 2 in the cation complexes reveals the aliphatic portion of the rings folded over the plane containing the heteroaromatic moiety with the ligands encapsulating the metal centre within their cavity by imposing. respectively, a square-based pyramidal and a square planar geometry. In both complexes, the metal ion completes its coordination sphere by interacting with a ClO4- ligand. The compound [Cu(L-3)(2)](PF6)(2) (4) containing a 1:2 cation complex was also isolated at the solid state: EPR spectroscopy measurements suggest the presence of a CuN4 chromophore in this complex. The EPR and electronic spectral features of 1-4 have been studied and their redox properties examined in comparison with those observed for Type-1 blue copper proteins.The reactivity of L-1-L-3 has also been tested toward stoichiometric amounts of the Cut salt [CuCl(PPh3)(3)], (c) 2005 Elsevier B.V. All rights reserved.