Nucleophilic substitution: a charge density perspective.
Nucleophilic substitution: a charge density perspective.
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亲核取代：电荷密度视角。
DOI：
10.1021/jp302087n
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发表时间：
2012
期刊：
影响因子：
--
通讯作者：
T. Jones
中科院分区：
文献类型：
--
作者：
T. Jones
亲核反应的一般描述是使用键丛来描述的，键丛是分子中原子量子理论的扩展，允许预测芳环的新的活化基。研究发现，反应活性与底物和离开基团之间的键束形状以及非键区的存在有关。封闭的键束比开放的键束活性更强，而非键区也增加了反应性。这种方法的优点是它可以用来研究所有的分子和固态体系。举个例子，我用这个模型来解释两个反常的反应体系：应变杂环和硫化物活化的芳香环。
A general description of nucleophilic reactions is developed using bond bundles, an extension of the quantum theory of atoms in molecules, allowing novel activating groups to be predicted for aromatic rings. Reactivity is found to be related to both the shape of the bond bundle between the substrate and leaving group and the presence of nonbonding regions. Closed bond bundles are shown to be more reactive than open ones, while nonbonding regions also increase reactivity. The advantage of this approach is that it can be employed to investigate all molecular and solid-state systems. By way of example I use this model to rationalize two anomalously reactive systems: strained heterocyclic rings and sulfide-activated aromatic rings.