Copper(I) Complexes with Thiourea Derivatives as Ligands: Revealing Secrets of Their Bonding Scheme
Copper(I) Complexes with Thiourea Derivatives as Ligands: Revealing Secrets of Their Bonding Scheme
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DOI：
10.1002/ejic.201601547
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发表时间：
2017-03-03
影响因子：
2.3
通讯作者：
Herres-Pawlis, Sonja
中科院分区：
文献类型：
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作者：
Hollmann, Katharina;Oppermann, Alexander;Herres-Pawlis, Sonja
合成并表征了五种不对称取代硫脲铜配合物。这包括两种配位聚合物[Cu（（SNH）-N-tu）Br]（n）和[Cu（S-tu（Py）NH）Br]（n），两种双核配合物[Cu-2（（SNH）-N-tu）（4）Br-2]和[Cu-2（S-tu（Py）NH）（2）Br-2（MeCN）（2）]，以及一种六核配合物[Cu-6（（SN）-N-tu）（6）]。配位聚合物的铜原子通过交替的溴桥和溴桥连接，二聚体结构通过溴桥连接。硫桥结构显示出与生物高度相关的CuA中心在其完全还原的氧化态的相似性。三个配合物进一步研究，通过使用DFT，包括一个完整的轨道分析，利用片段轨道（FO）和重叠人口（OP）。的双核配合物的键合图案是类似的CuA配合物，而六核物种的分析表明，对核心的配体的影响，因此对它的电子结构。此外，还对相关的双核和六核铜硫体系进行了比较分析.
We have synthesized and characterized five copper(I) complexes with unsymmetrically substituted thiourea ligands. These include two coordination polymers, [Cu((SNH)-N-tu)Br](n) and [Cu(S-tu(Py)NH)Br](n), two dinuclear complexes, [Cu-2((SNH)-N-tu)(4)Br-2] and [Cu-2(S-tu(Py)NH)(2)Br-2(MeCN)(2)], and one hexanuclear complex, [Cu-6((SN)-N-tu)(6)]. The Cu atoms of the coordination polymers are connected through alternating thione and bromide bridges and the dimeric structures through thione bridges. The thionebridged structures show similarities with the biologically highly relevant CuA center in its fully reduced oxidation state. Three of the complexes were further investigated by using DFT, including a full orbital analysis utilizing fragment orbitals (FOs) and overlap populations (OPs). The bonding motifs of the dinuclear complexes are similar to that of the CuA complex, whereas the analysis of the hexanuclear species showed the influence of the ligands on the core and hence on its electronic structure. Moreover, a comparative analysis of related dinuclear and hexanuclear copper- sulfur systems is presented.