Unraveling mechanisms of the uncoordinated nucleophiles: theoretical elucidations of the cleavage of bis(p-nitrophenyl) phosphate mediated by zinc-complexes with apical nucleophiles.
Unraveling mechanisms of the uncoordinated nucleophiles: theoretical elucidations of the cleavage of bis(p-nitrophenyl) phosphate mediated by zinc-complexes with apical nucleophiles.
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解开不配位亲核试剂的机制：通过锌配合物与顶端亲核试剂介导的双（对硝基苯基）磷酸酯裂解的理论阐明
DOI：
10.1039/c9ra06737j
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发表时间：
2019-11-19
期刊：
影响因子：
3.9
通讯作者：
Zhao, Cunyuan
中科院分区：
文献类型：
--
作者：
Zhou, Xiaoyu;Zhang, Xue-Peng;Li, Weikang;Jiang, Jingxing;Xu, Huiying;Ke, Zhuofeng;Phillips, David Lee;Zhao, Cunyuan
用理论方法研究了具有非配位亲核试剂的锌(II)配合物催化双(对硝基苯基)磷酸(BNP-−)的水解裂解机理。提出了基于配体和基于替代溶剂的亲核攻击反应模型。结果表明，[Zn(LnH)(η-H2O)(H2O)]2+(n=1，2，3)络合物中锌(II)结合水分子或配体的pKa值以及单核锌(II)络合物的二聚化倾向对反应机理有显著影响。研究发现，锌(II)-L3络合物更有利于BNPP−通过配体亲核攻击途径进行水解性切割。这是由于肟配体的去质子化的pKa值较低，单核锌(II)-L3物种的硬二聚，以及非配位亲核试剂的存在。系统地阐明了非配位反应的原因。本文报道的理论结果与实验结果吻合较好，更重要的是有助于阐明影响配位/非配位亲核试剂分子间亲核攻击反应的因素。用理论方法研究了具有非配位亲核试剂的锌(II)配合物催化双(对硝基苯基)磷酸(BNP-−)的水解裂解机理。
A theoretical approach was used to investigate the hydrolytic cleavage mechanisms of the bis(p-nitrophenyl) phosphate (BNPP−) catalyzed by Zn(ii)-complexes featuring uncoordinated nucleophiles. Ligand-based and alternative solvent-based nucleophilic attack reaction models are proposed. The pKa values of the Zn(ii)-bound water molecules or ligands in the [Zn(LnH)(η-H2O)(H2O)]2+ (n = 1, 2 and 3) complexes, as well as the dimerization tendency of the mononuclear Zn(ii)-complexes, were found to significantly influence the reaction mechanisms. The Zn(ii)-L3 complexes were found to be more favorable for the hydrolytic cleavage of the BNPP−via a ligand-based nucleophilic attack pathway. This was due to the lower pKa value for the deprotonation of the oxime ligand, the hard dimerization of the mononuclear Zn(ii)-L3 species, and the presence of an uncoordinated nucleophile. The origins of the uncoordinated reactions were systematically elucidated. The theoretical results reported here are in good agreement with experimental observations and more importantly, help to elucidate the factors that influence intermolecular nucleophilic attack reactions with coordinated/uncoordinated nucleophiles. A theoretical approach was used to investigate the hydrolytic cleavage mechanisms of the bis(p-nitrophenyl) phosphate (BNPP−) catalyzed by Zn(ii)-complexes featuring uncoordinated nucleophiles.
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影响因子：
4.4
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