In recent years, while main-group elements from the s- and p-block have emerged in the field of N2 activation, silylenes─despite their remarkable successes in the activation of diverse small molecules─remain unreported for N2 activation. Herein, we design “silylene-borole” frustrated Lewis pairs (FLPs) by combining silylene moieties with boron components and conduct comprehensive density functional theory (DFT) calculations to thoroughly investigate their potential for N2 activation. Screening silylene moieties via machine learning suggests that a smaller ΔEST value will benefit N2 activation thermodynamically. Interestingly, all these designed novel FLPs were found to be kinetically and thermodynamically favorable for N2 activation, exhibiting low reaction barriers (ranging from 16.9 to 22.5 kcal/mol) and significant exergonicity, with ΔG values ranging from −32.3 to −36.7 kcal/mol. The notable thermodynamic stability of the products, enhanced by aromaticity, coupled with low activation barriers, represents a pivotal advancement in the development of FLP-chemistry for metal-free N2 activation.

https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c02343