A Sophisticated Approach towards a New Class of Copper(I)–Sulfur Cluster Complexes with Imidazolinium–Dithiocarboxylate Ligands
A Sophisticated Approach towards a New Class of Copper(I)–Sulfur Cluster Complexes with Imidazolinium–Dithiocarboxylate Ligands
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DOI：
10.1002/ejic.201700328
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发表时间：
2017-07
影响因子：
2.3
通讯作者：
Jochen Ortmeyer;U. Flörke;G. Henkel;R. Wilhelm;A. Neuba
中科院分区：
文献类型：
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作者：
Jochen Ortmeyer;U. Flörke;G. Henkel;R. Wilhelm;A. Neuba
作为一个贡献，更好地理解咪唑啉-二硫代羧酸配体对铜的配位性能，第一条路线走向寡铜甜菜碱配合物已被开发。用不同比例的六氟磷酸铊（I）处理悬浮在乙腈中的配位聚合物[CuCl（Bz 2 ImCS 2）]n（1），得到离散的铜（I）簇阳离子[Cu 4（Bz 2 ImCS 2）4Cl 2]2+（2）和[Cu 3（Bz 2 ImCS 2）5]3+（3）。2（PF 6）2 2 MeCN和3（PF 6）3 2 MeCN Et 2 O的单晶X射线衍射揭示了独特的铜-硫结构的存在。2的Cu-S/Cl骨架包含两个细长的三棱柱{Cu 4S 2}实体，它们共享一个共同的{Cu 4}面。相比之下，Cu原子3定义了一个等腰三角形。这两种化合物均表现出基于S3 Cl（2内）和S4（3内）供体组和宿主二硫代羧酸盐两性离子的扭曲四面体铜配位位点，每个配位模式均不同。总的来说，这里提出了三种不同类型的对铜的结合原理。
As a contribution to a better understanding of the coordination properties of imidazolinium-dithiocarboxylate ligands towards copper, the first route towards oligonuclear copper-betaine complexes has been developed. Treatment of the coordination polymer [CuCl(Bz2ImCS2)]n (1) suspended in acetonitrile with thallium(I)-hexafluorophosphate in different ratios affords the discrete copper(I) cluster cations [Cu4(Bz2ImCS2)4Cl2]2+(2) and [Cu3(Bz2ImCS2)5]3+ (3). Single crystal X-ray diffraction of 2(PF6)2 ∙ 2 MeCN and 3(PF6)3 ∙ 2 MeCN ∙ Et2O reveals the occurrence of unique copper-sulfur architectures. The Cu-S/Cl skeleton of 2 contains two elongated trigonal-prismatic {Cu4S2} entities which share a common {Cu4} face. In contrast, the Cu atoms of 3 define an isosceles triangle. Both compounds exhibit distorted tetrahedral copper coordination sites based on S3Cl (within 2) and S4 (within 3) donor sets and host dithiocarboxylate zwitterions in two different coordination modes each. Overall, three different types of binding principles towards copper are presented here.