Quantitative reactivity model for the hydration of carbon dioxide by biomimetic zinc complexes

被引：80

作者：

Brauer, M

Pérez-Lustres, JL

Weston, J

Anders, E ^{[1
]}

机构：

[1] Univ Jena, Inst Organ Chem & Makromol Chem, D-07743 Jena, Germany

[2] Univ Santiago Compostela, Fac Quim, Dept Quim Fis, E-15706 Santiago, Spain

[3] Continental AG, D-30419 Hannover, Germany

来源：

INORGANIC CHEMISTRY | 2002年 / 41卷 / 06期

关键词：

D O I：

10.1021/ic0010510

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A quantitative structure-reactivity relationship has been derived from the results of B3LYP/6-311+G* calculations on the hydration of carbon dioxide by a series of zinc complexes designed to mimic carbonic anhydrase. The reaction mechanism found is general for all complexes investigated. The reaction exhibits a low (4-6 kcal/mol) activation energy and is exothermic by about 8 kcal/mol. The calculations suggest an equilibrium between Lipscomb and Lindskog intermediates. The effectiveness of the catalysis is a function of the nucleophilicity of the zinc-bound hydroxide and the nucleofugicity of the zinc-bound bicarbonate. Hydrogen bridging of the bicarbonate to NH moieties in the ligands also plays an important role.

引用

页码：1454 / 1463

页数：10

共 81 条

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