Although the carbene-catalyzed N2 fixation process had been investigated by scientists for decades prior to borylene species, the interest in the carbene-mediated N2 activation process has drawn less attention than that of borylene species in the past few years, especially unique σ0π2 carbenes. Herein, we demonstrate the important role of unique σ0π2 carbenes in the 1,1-hydroboration and bis-carbene functionalization of N2 using density functional theory calculations. Both being kinetically and thermodynamically favorable, the reaction barriers are as low as 13.7 and 16.6 kcal/mol, respectively. Additionally, such a σ0π2 carbene can also achieve a series of X–H insertion reactions (X = H, CH3, Bpin, or SiH2Ph), with activation energies ranging from 8.2 to 15.3 kcal/mol. Our findings highlight a strong potential of carbenes with σ0π2 electronic configuration in N2 activation and its versatile transformations, providing valuable insights into main-group-element-mediated N2 activation chemistry.

https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00726