Electrophilicity and Nucleophilicity of Boryl Radicals.

Abstract

We carried out a survey of the relative reactivity of a collection of 91 neutral boryl radicals using density functional calculations. Their reactivities were characterized by four indices, i.e., the global electrophilicity, global nucleophilicity, local electrophilicity, and local nucleophilicity. Particularly, the global electrophilicity and nucleophilicity indices span over a moderately wider range than those of carbon radicals, indicating their potentially broader reactivity. Thus, boryl radicals may be utilized in electrophilic radical reactions, while traditionally they are only considered for nucleophilic radical reactions. In contrast, the local electrophilicity and nucleophilicity indices at the boron center show a different reactivity picture than their global counterparts. The inconsistency is rooted in the low and varying spin density on boron (for most radicals, less than 50%) in different boryl radicals, which is a combinative result of radical stabilization via electron delocalization and the low electronegativity of boron (compared to carbon). In short, the boron character in boryl radicals may be weak and their reactivity is not reflected by the local indices based on boron but by the global ones.