FACTORS DETERMINING NUCLEOPHILIC REACTIVITIES
FACTORS DETERMINING NUCLEOPHILIC REACTIVITIES
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DOI：
10.1021/ja00860a005
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发表时间：
1962-01-01
影响因子：
15
通讯作者：
PEARSON, RG
中科院分区：
文献类型：
--
作者：
EDWARDS, JO;PEARSON, RG
考虑了决定亲核试剂反应性的三个重要因素。它们是碱性、极化率和与亲核原子相邻的原子上的非共享电子对的存在，即α效应。讨论了这三个因素的理论基础。给出了一些底物的实验数据，这些数据表明，某些底物的反应性几乎完全取决于亲核试剂的碱性，而某些底物的反应性完全取决于极化率。类似于质子的基质具有高正电荷和中心原子外轨道中的低电子数，这取决于碱度。具有低正电荷和在中心原子的外轨道中具有许多电子的基底取决于极化率。α效应似乎是一般的所有基板。
Three important factors determining the reactivity of nucleophilic reagents are considered. These are basicity, polarizabil-ity and the presence of unshared pairs of electrons on the atom adjacent to the nucleophilic atom, the alpha effect. The theoretical bases for these three factors are discussed. Experimental data for a number of substrates are given which make it clear that the reactivities of some substrates depend almost entirely on basicity of the nucleophile, and some substrate reactivities depend entirely on the polarizability. Substrates which resemble the proton in having a high positive charge and a low number of electrons in the outer orbitals of the central atom depend on basicity. Substrates with a low positive charge and with many electrons in the outer orbitals of the central atom depend on polarizability. The alpha effect appears to be general for all substrates.