Formation and reactivity of NHC-boryl radicals: insight into substituent effect from theoretical calculations

Substituent modification effects of N-heterocyclic carbene (NHC) boranes on their hydrogen atom abstraction (HAA) reactions and the chemical reactivities of corresponding NHC-boryl radicals have been investigated by density functional theory calculations. The substituent modification of NHC-boranes may notably affect the HAA reaction, both kinetically and thermodynamically, and shows remarkable substitution position dependence. The multi-site-modification of NHC-boranes is proved to be more effective for reduction of the B-H bond dissociation energy (BDE), promotion of the HAA reaction, and the reactivity regulation of their corresponding NHC-boryl radicals. Computational screening reveals that the spin density and the charge population of the radical boron center have good correlation with the B-H BDEs of NHC-boranes and the chemical reactivities of NHC-boryl radicals, and they can be considered as property and reactivity descriptors of these boron-based systems. The present results and established scaling relationships are beneficial to promote the advancement of design of NHC-boryl radical catalysis.