A DFT study on the mechanism of phosphodiester cleavage mediated by monozinc complexes
A DFT study on the mechanism of phosphodiester cleavage mediated by monozinc complexes
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DOI：
10.1021/ja0660251
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发表时间：
2007-01-31
影响因子：
15
通讯作者：
Gao, Yi Qin
中科院分区：
文献类型：
--
作者：
Fan, Yubo;Gao, Yi Qin
采用密度泛函理论（DFT）， Tao-Perdew-Staroverov-Scuseria （TPSS）研究了锌介导的磷酸二酯裂解反应的反应机理。计算结果表明碱催化机理一般。锌（II）离子配位数（5和6）的柔韧性以及配位水与酯之间氢键的形成是磷二酯捕获（即与锌配合物配位）的原因。水、酯和氮配体三（6-氨基-2-吡啶基甲基）胺之间的氢键不仅稳定了具有三角金字塔结构的PO5单元的关键五配位磷中间体，而且通过获得更强的溶剂化能，降低了配合物内质子转移的能垒。
Density functional theory (DFT), Tao-Perdew-Staroverov-Scuseria (TPSS), is employed to study the reaction mechanism for the zinc-mediated phosphodiester cleavage reaction. The calculations indicate a general base catalysis mechanism. The flexibility of Zn(II) ion's coordination number (5 and 6) as well as the formation of hydrogen bonds between the coordinating water and the ester are responsible for the trapping (namely, coordinating to the Zn complexes) of the phosphodiester. The hydrogen bonds, between the water, the ester, and the nitrogen-ligand, tris(6-amino-2-pyridylmethyl)amine, not only stabilize the key five-coordinated phosphorus intermediates with a trigonal pyramidal PO5 unit but also lower the energy barriers for the proton transfer within the complexes by gaining stronger solvation energies.