Dinitrogen (N2) activation is particularly challenging under ambient conditions because of its large highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap (10.8 eV) and high bond dissociation energy (945 kJ mol–1) of the NΞN triple bond, attracting considerable attention from both experimental and theoretical chemists. However, most effort has focused on metallic systems. In contrast, nitrogen activation by frustrated Lewis pairs (FLPs) has been initiated recently via theoretical calculations.

Transfer hydrogenation of azobenzene with ammonia borane mediated by pincer bismuth complex 1 were systematically investigated through density functional theory calculations. An unusual metal-ligand cooperation mechanism was disclosed, in which the saturation/regeneration of the C=N functional group on the pincer ligand plays an essential role. The reaction is initiated by the hydrogenation of the C=N bond (saturation) with ammonia borane to afford 3CN, which is the rate-determining step with Gibbs energy barrier (ΔG≠) and Gibbs reaction energy (ΔG) of 25.6 and -7.3 kcal/mol, respectively.

For decades, N2 activation and functionalization have required the use of transition metal complexes. Thus, it is one of the most challenging projects to activate the abundant dinitrogen through metal-free systems under mild conditions. Here, we demonstrate a proof-of-concept study on the catalytic hydrogenation of dinitrogen (with an activation energy as low as 15.3 kcal mol -1 ) initiated by a dual Lewis acid (DLA) via density functional theory (DFT) calculations.

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.

Due to consumption of more than 2% of the world's annual energy supply by Haber–Bosch process and the strongest triple bond (N≡N) in nature, directly coupling N 2 with small molecules is particularly important and challenging, let alone in a catalytic fashion. Here we first demonstrate that a NNN-type pincer phosphorus complex could act as a catalyst to couple dinitrogen with a series of small molecules including carbon dioxide, formaldehyde, N-ethylidenemethylamine, and acetonitrile in the presence of diborane(4) under a mild condition by theoretical calculations.

As the strongest triple bond in nature, the N≡N triple bond activation has always been a challenging project in chemistry. On the other hand, since the award of the Nobel Prize in Chemistry in 1950, Diels‐Alder reaction has served as a powerful and widely applied tool in the synthesis of natural products and new materials. However, the application of Diels‐Alder reaction to dinitrogen activation remains less developed.

Based on Hückel’s and Baird’s rules, species are aromatic either in the lowest singlet state (S0) or the lowest triplet state (T1) only. Thus, species with adaptive aromaticity (with aromaticity in both the S0 and T1 states) is particularly rare. On the other hand, σ-aromaticity in the T1 state has been underdeveloped, let alone adaptive σ-aromaticity. Herein, via various aromaticity indices including NICS, ACID and EDDB, we demonstrate adaptive s-aromaticity in an unsaturated three-membered ring, which is a traditional area dominated by π-aromaticity.

Discovery of species with adaptive aromaticity (being aromatic in both the lowest singlet and triplet states) is particularly challenging as cyclic species are generally aromatic either in the ground state or in the excited state only according to Hückel’s and Baird’s rules.

Carbon dioxide (CO2, a common combustion pollutant) releasing continuously into the atmosphere is primarily responsible for the rising atmospheric temperature. Therefore, CO2 sequestration has been an indispensable area of research for the past several decades. On the other hand, the concept of aromaticity is often employed in designing chemical reactions and metal‐free frustrated Lewis pairs (FLPs) have proved ideal reagents to achieve CO2 reduction. However, considering FLP and aromaticity together is less developed in CO2 capture.

Benzene, the prototype of aromatics, has six equivalent C‐C bonds (1.397 Å), which are intermediate between a C‐C double bond and a C‐C single bond. For over 80 years, chemists have spent much effort on freezing a localized structure to obtain a distorted bond‐length alternating benzene ring in the ground state, leading to various localized trisannelated benzene rings. However, most of the central benzene rings are still aromatic or nonaromatic. Here we report an antiaromatic benzene ring caused by hyperconjugation.