Citation: Jie Zeng, Jiaying Su, Feiying You, Jun Zhu. Understanding reaction mechanisms of metal-free dinitrogen activation by methyleneboranes[J]. Chinese Chemical Letters, ;2023, 34(2): 107759. doi: 10.1016/j.cclet.2022.107759 shu

Understanding reaction mechanisms of metal-free dinitrogen activation by methyleneboranes

State Key Laboratory of Physical Chemistry of Solid Surfaces and Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China

jun.zhu@xmu.edu.cn

Received Date: 7 June 2022
Revised Date: 8 August 2022
Accepted Date: 16 August 2022
Available Online: 19 August 2022

Figures(6)

Dinitrogen activation under mild conditions is important but extremely challenging due to the inert nature 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 activation, 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 NN triple bond. Our findings could be helpful for experimental chemists aiming at dinitrogen activation by main group species.
- Dinitrogen activation,
- Methyleneborane,
- NHC-stabilized borylene,
- Reaction mechanism,
- Singlet–triplet gap
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