Formation and stability of mononuclear and dinuclear Eu(III) complexes and their catalytic reactivity toward cleavage of an RNA analog

被引：38

作者：

Farquhar, Erik R. ^{[1
]}

Richard, John P. ^{[1
]}

Morrow, Janet R. ^{[1
]}

机构：

[1] SUNY Buffalo, Dept Chem, Amherst, NY 14260 USA

来源：

INORGANIC CHEMISTRY | 2007年 / 46卷 / 17期

关键词：

D O I：

10.1021/ic7005666

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The complex between Eu(III) and 1,7-diaza-4,10,13-trioxacyclopentadecane-N,N'-diacetic acid (1-4) was characterized by pH potentiometric titration and (1)H NMR spectroscopy. The conversion of the monomer to a dimeric complex is observed as the pH is increased from 7 to 10 in a reaction that releases one mol/HO(-) per dimer formed. The dimeric complex undergoes a further ionization with a pK(a) of 10.7. Kinetic parameters are reported for the cleavage of the simple phosphodiester 2-hydroxypropyl-4-nitrophenyl phosphate catalyzed by both the monomeric and the dimeric Eu(III) complexes. These data show that the monomer and dimer stabilize their bound reaction transition states with similar free energies of 7.1 and 7.6 kcal/mol, respectively. Clearly, a bridging hydroxide is not an optimal linker to promote cooperative catalysis between Eu(Ill) centers in macrocycles with multiple polyaminocarboxylate pendent groups.

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页码：7169 / 7177

页数：9

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