Dinuclear Complexes of Copper(I) with Crown Ether‐containing N ‐Thiophosphorylated Bis‐thioureas and 2,2′‐Bipyridine or 1,10‐Phenanthroline: Synthesis, Characterization, and Picrate Extraction Properties

Reaction of O , O′ ‐diisopropylthiophosphoric acid isothiocyanate ( i PrO) 2 P(S)NCS with 1,10‐diaza‐18‐crown‐6, 1,7‐diaza‐18‐crown‐6, or 1,7‐diaza‐15‐crown‐5 leads to the N ‐thiophosphorylated bis‐thioureas N , N′ ‐bis[C(S)NHP(S)(O i Pr) 2 ]‐1,10‐diaza‐18‐crown‐6 ( H 2 L I ), N , N′ ‐bis[C(S)NHP(S)(O i Pr) 2 ]‐1,7‐diaza‐18‐crown‐6 ( H 2 L II ) and N , N′ ‐bis[C(S)NHP(S)(O i Pr) 2 ]‐1,7‐diaza‐15‐crown‐5 ( H 2 L III ). Reaction of the potassium salts of H 2 L I–III with a mixture of CuI and 2,2′‐bipyridine ( bpy ) or 1,10‐phenanthroline ( phen ) in aqueous EtOH/CH 2 Cl 2 leads to the dinuclear complexes [Cu 2 (bpy) 2 L I–III ] and [Cu 2 (phen) 2 L I–III ] . The structures of these compounds were investigated by 1 H, 31 P{ 1 H} NMR spectroscopy, and elemental analysis. The crystal structures of H 2 L I and [Cu 2 (phen) 2 L I ] were determined by single‐crystal X‐ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10‐diaza‐18‐crown‐6, N , N′ ‐bis[C(=CMe 2 )CH 2 P(O)(O i Pr) 2 ]‐1,10‐diaza‐18‐crown‐6, N , N′ ‐bis[C(S)NHP(O)(O i Pr) 2 ]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH 4 Pic were also studied.