Screening seven-electron boron-centered radicals for dinitrogen activation.

The activation of dinitrogen is significant as nitrogen-containing compounds play an important role in industries. However, the inert NN triple bond caused by its large HOMO-LUMO gap (10.8 eV) and high bond dissociation energy (945 kJ mol-1 ) renders its activation under mild conditions particularly challenging. Recent progress shows that a few main group species can mimic transition metal complexes to activate dinitrogen. Here, we demonstrate that a series of seven-electron (7e) boron-centered radical can be used to activate N2 via density functional theory calculations. It is found that boron-centered radicals containing amine ligand perform best on the thermodynamics of dinitrogen activation. In addition, when electron-donating groups are introduced at the boron atom, these radicals can be used to activate N2 with low reaction barriers. Further analysis suggests that the electron transfer from the boron atom to the π* orbitals of dinitrogen is essential for its activation. Our findings suggest great potential of 7e boron radicals in the field of dinitrogen activation.

Theoretical Study on Reaction Mechanisms of Dinitrogen Activation and Coupling by Carbene-Stabilized Borylenes in Comparison with Intramolecular C-H Bond Activation.

Dinitrogen (N2 ) activation is particularly challenging due to the significantly strong N≡N bond, let alone the catenation of two N2 molecules. Recent experimental study shows that cyclic (alkyl)(amino)carbene (CAAC)-stabilized borylenes are able to tackle N2 activation and coupling below room temperature. Here we carry out density functional theory calculations to explore the corresponding reaction mechanisms. The results indicate that the reaction barrier for the dinitrogen activation by the first borylene is slightly higher than that by the second borylene. In addition, replacing the CAAC moiety of the borylenes with cyclic diaminocarbenes (CDACs) could make such dinitrogen activation and coupling more favorable thermodynamically. The reaction mechanisms of the intramolecular C-H bond activation of borylene have also been discussed, which is found to be favorable both thermodynamically and kinetically in comparison with N2 activation. Thus, adequate attention should be paid to the design of borylenes aiming at N2 activation. In addition, our calculations suggest that the CDAC moiety of the borylene could lead to a different product in terms of intramolecular C-H bond activation. All these findings could be useful for the development of dinitrogen activation as well as C-H bond activation by main group species.

Direct Conversion of N2 and O2 to Nitric Oxide at Room Temperature Initiated by Double Aromaticity in the Y2BO+ Cation.

The conversion of dinitrogen to more useful and reactive molecules has been the focus of intense research by chemists. In contrast to reductive N2 fixation, direct oxidation of N2 by O2 to nitric oxide under mild conditions via a thermochemical process is extremely challenging. Herein, we report the first example of N2 and O2 activation and coupling under thermochemical conditions through the remarkable ability of Y2BO+ to react with one N2 and two O2 molecules. Detailed mechanistic studies using mass spectrometry and quantum chemical calculations revealed that the N2 activation by Y2BO+ is facilitated by the double aromatic character of the Y2BON2+ intermediate. Subsequent oxidation with O2 releases NO in a dearomatization process driven by the formation of stronger Y-O bonds over the Y-N bonds. Our findings represent the first example of N2 and O2 activation and coupling under thermochemical conditions at room temperature, providing a novel strategy for small-molecule activation.