A Sophisticated Approach towards a New Class of Copper(I) Sulfur Cluster Complexes with Imidazolinium-dithiocarboxylate Ligands

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.

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