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

被引：79
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.
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收藏
页码：1454 / 1463
页数：10
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