Interaction of Mixed-Donor Macrocycles Containing the 1,10-Phenanthroline Subunit with Selected Transition and Post-Transition Metal Ions: Metal Ion Recognition in Competitive Liquid−Liquid Solv

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• 作者：M. Carla Aragoni ; Massimiliano Arca ; Andrea Bencini ; Silvia Biagini ; Alexander J. Blake ; Claudia Caltagirone ; Francesco Demartin ; Greta De Filippo ; Francesco A. Devillanova ; Alessandra Garau ; Karsten
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：September 15, 2008
• 年：2008
• 卷：47
• 期：18
• 页码：8391-8404
• 全文大小：402K
• 年卷期：v.47,no.18(September 15, 2008)
• ISSN：1520-510X

文摘

Two new mixed aza-thia crowns 5-aza-2,8-dithia[9]-(2,9)-1,10-phenanthrolinophane (L⁴) and 2,8-diaza-5-thia[9]-(2,9)-1,10-phenanthrolinophane (L⁷) have been synthesized and characterized. The coordination behavior of L⁴ and L⁷ toward the metal ions Cu^II, Zn^II, Pb^II, Cd^II, Hg^II, and Ag^I was studied in aqueous solution by potentiometric methods, in CD₃CN/D₂O 4:1 (v/v) by ¹H NMR titrations and in the solid state. The data obtained were compared with those available for the coordination behavior toward the same metal ions of structurally analogous mixed donor macrocyclic ligands L¹-L³, L⁵, L⁶: all these contain a phenanthroline subunit but have only S/O/N(aromatic) donor groups in the remaining portion of the ring and are, therefore, less water-soluble than L⁴ and L⁷. The complexes [Cd(NO₃)₂(L⁵)], [Pb(L⁷)](ClO₄)₂·¹/₂MeCN, [Pb(L⁴)](ClO₄)₂·MeCN, and [Cu(L⁷)](ClO₄)₂·³/₂MeNO₂ were characterized by X-ray crystallography. The efficacy of L¹-L⁷ in competitive liquid−liquid metal ion extraction of Cu^II, Zn^II, Cd^II, Pb^II, Ag^I, and Hg^II was assessed. In the absence of Hg^II, a clear extraction selectivity for Ag^I was observed in all systems investigated.