Metal Ion Dependent Molecular Inclusion Chemistry: Inclusion of p-Toluenesulfonate and p-Nitrophenolate within the Structure of Coordinated 1,4,7,10-Tetrakis((S)-2-hydroxy-3-pheno

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• 作者：Christopher B. Smith ; Kia S. Wallwork ; Jennifer M. Weeks ; Mark A. Buntine ; Stephen F. Lincoln ; Max R. Taylor ; and Kevin P. Wainwright
• 刊名：Inorganic Chemistry
• 出版年：1999
• 出版时间：November 1, 1999
• 年：1999
• 卷：38
• 期：22
• 页码：4986 - 4992
• 全文大小：121K
• 年卷期：v.38,no.22(November 1, 1999)
• ISSN：1520-510X

文摘

The pendant donor macrocyclic ligand 1,4,7,10-tetrakis((S)-2-hydroxy-3-phenoxypropyl)-1,4,7,10-tetraazacyclododecane ((S)-thphpc12) has been synthesized in quantitative yield from cyclen (1,4,7,10-tetraazacyclododecane)and (2S)-(+)-3-phenoxy-1,2-epoxypropane. An X-ray diffraction study supports the result of molecular orbitalcalculations in showing that complexation with hydrated cadmium(II) diperchlorate produces an approximatelysquare-antiprismatic complex in which the metal ion is located between a plane containing the four nitrogenatoms and a plane containing the four oxygen atoms. As a consequence of this the four phenoxymethyl moieties,each attached to one of the four N-O chelate rings, juxtapose to form a substantial empty cavity allowing thecomplex to act as a molecular receptor. Inclusion complexes have been formed from this complex in which eithera p-toluenesulfonate or p-nitrophenolate anion has entered the cavity. An X-ray crystallographic study of [Cd((S)-thphpc12)(p-toluenesulfonate)]ClO₄ shows that the guest anion is retained within the cavity by four hydrogenbonds to the group of hydroxyl moieties associated with the ligand. ¹³C NMR and conductivity studies indicatethat this inclusion complex retains its integrity in DMSO or DMF solution. Parallel studies have been conductedwith [Pb((S)-thphpc12)](ClO₄)₂ indicating that the corresponding inclusion complexes are of lower stability.