The known reactions between a neutral radical and a neutral closed-shell σ-type molecule are generally associated with the atom/group-abstraction (e.g., CN, OH reactions) or the carbenoid insertion processes (e.g., CH reactions). In this article, we describe a new type of neutral radical-molecule reaction that feature the nucleophilic addition and elimination mechanism based on the systematic Gaussian-3//MP2(full)/6-31G(d) investigations on the PH 3 CH+HX model reactions (X = CH 3 , NH 2 , OH, F, CH 2 F, CHF 2 , CF 3 , NHCH 3 /CH 2 NH 2 , OCH 3 /CH 2 OH). The novel properties are found to benefit both from the radical and ylidic characters of PH 3 CH, and the type of reagent HX determines the nucleophilic addition reactivity. The present work is the first study on the chemical reactivity of the ylidic radicals.
['Hong-Bin Xie', 'Yi-hong Ding', 'Chia-Chung Sun']
Ylidic radical–molecule reactions