Understanding reaction mechanisms of metal-free dinitrogen activation by methyleneboranes

Dinitrogen activation under mild conditions is important but extremely challenging due to the inert na-ture of the N =N triple bond evidenced by high bond dissociation energy (945 kJ/mol) and large HOMO-LUMO gap (10.8 eV). In comparison with largely developed transition metal systems, the reported main group species on dinitrogen activation are rare. Here, we carry out density functional theory calculations on methyleneboranes to understand the reaction mechanisms of their dinitrogen activation. It is found that the methyleneboranes without any substituent at the boron atom performs best on dinitrogen ac-tivation, which could be contributed to its small singlet-triplet gap. In addition, strong correlations are achieved on dinitrogen activation between the singlet-triplet energy gap and the reaction energies for the formation of the end-on products as well as the side-on ones. The principal interacting orbital analysis suggests that methyleneboranes can mimic transition metals to cleave the N =N triple bond. Our findings could be helpful for experimental chemists aiming at dinitrogen activation by main group species.(c) 2022 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Automated summary

It is found that methyleneboranes without any substituent at the boron atom perform best on dinitrogen activation due to their small singlet-triplet gap. Strong correlations are achieved between the singlet-triplet energy gap and the reaction energies for the formation of end-on and side-on products. Methyleneboranes can mimic transition metals to cleave the N=N triple bond, which is important for experimental chemists studying dinitrogen activation by main group species.