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首页> 外文期刊>RSC Advances >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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Unraveling mechanisms of the uncoordinated nucleophiles: theoretical elucidations of the cleavage of bis(p-nitrophenyl) phosphate mediated by zinc-complexes with apical nucleophiles

机译：未配位亲核试剂的解开机理：锌配合物与顶端亲核试剂介导的磷酸双（对硝基苯基）酯裂解的理论解释

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摘要

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 p K _(a) values of the Zn( II )-bound water molecules or ligands in the [Zn(L ~( n ) H)(η-H _(2) O)(H _(2) O)] ~(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 )-L ~(3) 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 p K _(a) value for the deprotonation of the oxime ligand, the hard dimerization of the mononuclear Zn( II )-L ~(3) 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.
机译：采用一种理论方法研究了具有不配位亲核试剂的Zn（II）配合物催化的磷酸对双（对硝基苯基）酯（BNPP〜（α））的水解裂解机理。提出了基于配体和替代溶剂的亲核攻击反应模型。 [Zn（L〜（n）H）（η-H_（2）O）（H _（2）O）中与Zn（II）结合的水分子或配体的p K _（a）值发现]〜（2+）（n = 1、2和3）配合物以及单核Zn（II）配合物的二聚化趋势显着影响反应机理。发现Zn（II）-L〜（3）配合物更有利于通过基于配体的亲核攻击途径水解BNPP〜（α）。这是由于肟配体的去质子化，单核Zn（II）-L〜（3）物种的硬二聚和较低的亲核试剂存在而导致的较低的p K_（a）值。系统地阐明了不协调反应的起源。此处报道的理论结果与实验观察结果非常吻合，更重要的是，有助于阐明影响配位/不配位亲核试剂的分子间亲核进攻反应的因素。

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