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

Reaction 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 (H 2LI), 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/CH 2Cl2 leads to the dinuclear complexes [Cu 2(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. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.