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

作者：Babashkina Maria G; Shakirova Elmira R; Safin Damir A^*; Sokolov Felix D; Klein Axel; Szyrwiel Lukasz; Kubiak Maria; Kozlowski Henryk; Krivolapov Dmitriy B

来源：Zeitschrift fur Anorganische und Allgemeine Chemie, 2010, 636(15): 2626-2632.

DOI：10.1002/zaac.201000263

• Copper
• X-ray diffraction
• N-Thiophosphoryl bis-thiourea
• 2,2 '-Bipyridine
• 1,10-Phenanthroline

Reaction of O,O`-diisopropylthiophosphoric acid isothiocyanate (iPrO)(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)(OiPr)(2)]-1,10-diaza-18-crown-6 (H2L1), 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 Cul and 2,2`-bipyridine (bpy) or 1,10-phenanthroline (phen) in aqueous EtOH/CH2Cl2 leads to the dinuclear complexes [Cu-2(bPY)(2)LI-III] and [Cu-2(Phen)(2)LI-III]. The structures of these compounds were investigated by H-1, P-31{H-1} NMR spectroscopy, and elemental analysis. The crystal structures of H2L1 and [Cu-2(phen)(2)L-1] 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 NH(4)Pic were also studied.

• 出版日期2010