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

Abstract

AbstractReaction of O,O′‐diisopropylthiophosphoric acid isothiocyanate (iPrO)2P(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)(OiPr)2]‐1,10‐diaza‐18‐crown‐6 (H2LI), N,N′‐bis[C(S)NHP(S)(OiPr)2]‐1,7‐diaza‐18‐crown‐6 (H2LII) and N,N′‐bis[C(S)NHP(S)(OiPr)2]‐1,7‐diaza‐15‐crown‐5 (H2LIII). Reaction of the potassium salts of H2LI–III with a mixture of CuI and 2,2′‐bipyridine (bpy) or 1,10‐phenanthroline (phen) in aqueous EtOH/CH2Cl2 leads to the dinuclear complexes [Cu2(bpy)2LI–III] and [Cu2(phen)2LI–III]. The structures of these compounds were investigated by 1H, 31P{1H} NMR spectroscopy, and elemental analysis. The crystal structures of H2LI and [Cu2(phen)2LI] 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(=CMe2)CH2P(O)(OiPr)2]‐1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(S)NHP(O)(OiPr)2]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH4Pic were also studied.