Predicting Activation of Small Molecules Including Dinitrogen via a Carbene with a σ0π2 Electronic Configuration

Although the main group species in the s and p blocks have begun to gain prominence in the field of dinitrogen (N 2 ) activation in recent years, reports of carbene-mediated N 2 activation remain particularly rare, especially for carbenes with a σ 0 π 2 electronic configuration. Herein, we demonstrate examples of N 2 activation initiated by a carbene with a σ 0 π 2 electronic configuration and consequent N 2 hydroboration reaction (with a reaction barrier as low as 19.9 kcal/mol) via density functional theory calculations. Meanwhile, the “push–pull” electronic effect upon introduction of a hydroborenium complex facilitates the generation of a thermodynamically and kinetically more stable product. In addition, such a σ 0 π 2 carbene can also activate a series of H–X (X = H, CH 3, or Bpin) bonds through an oxidative addition process with activation energies ranging from 6.0 to 18.0 kcal/mol. Our findings highlight the importance of σ 0 π 2 carbenes in the field of small molecule activation, especially N 2 activation.