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诱导效应

誘導效應,即因分子原子基團極性电負性)不同而致使成键电子雲在原子链上向某一方向移动的效應。其本质是静电感應。电子雲偏向电负性较强的基团或原子(如)移动。

诱导效应的强弱程度可以通过测量偶极矩而得知,也可以通过比较相关取代羧酸酸解离常数而大致估量。它随距离的增长而迅速下降,故一般情况下只需要考虑三根键的影响。诱导效应的另外一个特点是电子云是沿原子链移动或传递的,这一点与场效应不同。

诱导作用的大小一般以为标准进行比较:吸电子能力比氢强的基团或原子具吸电子诱导效应,用 −I 表示;给电子能力比氢强的基团或原子则具给电子诱导效应,用 +I 表示。

取代基的诱导效应强弱有如下规律:

  • 同族元素中,原子序数越大,吸电子诱导效应越弱;同周期元素中,原子序数越大,吸电子诱导效应越强。
  • 基团不饱和程度越大,吸电子诱导效应越强。这是由于各杂化态中 s 轨道成分不同而引起的,s 成分越高,吸电子能力越强。
  • 正电荷基团和含配位键(直接相连)的基团具吸电子诱导效应,负电荷基团具给电子诱导效应。
  • 烷基具给电子诱导效应和给电子超共轭效应

常见基团的诱导效应顺序如下:

  • 拉电子基:NO2 > CN > F > COOH > Cl > Br > I > C≡C > OH > C6H5 > C=C > H
  • 推电子基:(CH3)3C- > (CH3)2CH- > CH3CH2- > CH3- > H

參考資料

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诱导效应
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