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A Sophisticated Approach towards a New Class of Copper(I)–Sulfur Cluster Complexes with Imidazolinium–Dithiocarboxylate Ligands
Author(s) -
Ortmeyer Jochen,
Flörke Ulrich,
Henkel Gerald,
Wilhelm René,
Neuba Adam
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201700328
Subject(s) - chemistry , copper , crystallography , acetonitrile , cluster (spacecraft) , crystal structure , inorganic chemistry , organic chemistry , computer science , programming language
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(Bz 2 ImCS 2 )] n ( 1 ) suspended in acetonitrile with thallium(I) hexafluorophosphate in different ratios affords the discrete copper(I) cluster cations [Cu 4 (Bz 2 ImCS 2 ) 4 Cl 2 ] 2+ ( 2 ) and [Cu 3 (Bz 2 ImCS 2 ) 5 ] 3+ ( 3 ). Single‐crystal X‐ray diffraction of 2 (PF 6 ) 2 · 2MeCN and 3 (PF 6 ) 3 · 2MeCN · Et 2 O reveals the occurrence of unique copper–sulfur architectures. The Cu–S/Cl skeleton of 2 contains two elongated trigonal‐prismatic {Cu 4 S 2 } entities which share a common {Cu 4 } face. In contrast, the Cu atoms of 3 define an isosceles triangle. Both compounds exhibit distorted tetrahedral copper coordination sites, based on S 3 Cl (within 2 ) and S 4 (within 3 ) donor sets, and host dithiocarboxylate zwitterions in each of two different coordination modes. Overall, three different types of binding principles towards copper are presented here.