The capture of carbon dioxide is extremely important due to the increasingly severe greenhouse effect, and the conversion of dinitrogen into high-value N–C compounds is of great significance. Here, we predict through density functional theory calculations that the coupling of dinitrogen with carbon dioxide by methyleneborane becomes favorable both thermodynamically and kinetically. Machine learning analysis suggests that increasing the HOMO–LUMO gap or the charge on the boron atom or decreasing the charge of the nitrogen atom will reduce the reaction energies.

N2 adsorption on metal sites under mild conditions and its dependence on the chemical environment are crucial for understanding the fundamental mechanism and designing an efficient catalyst. Here, electrospray ionization mass spectrometry (ESI-MS) experiments reveal distinct differences in N2 binding capabilities among nickel complexes: both [(acetylacetonato)Ni]+ and [(benzoylacetonato)Ni]+ gas-phase cations exhibit high N2 adsorption efficiency, while the bare Ni+ and [(benzoylacetone)Ni(acetonitrile)]+ cations show negligible reactivity toward N2.

Aromaticity is one of the fundamental concepts in chemistry and generally brings additional thermodynamic stability to a compound. On the other hand, boron radicals have attracted increasing interest from both theoretical and experimental chemists due to their various applications. Here, we carry out density functional theory (DFT) calculations to explore the relationship between the (anti)aromaticity and stability of boron-centered radicals.

Although the carbene-catalyzed N2 fixation process had been investigated by scientists for decades prior to borylene species, the interest in the carbene-mediated N2 activation process has drawn less attention than that of borylene species in the past few years, especially unique σ0π2 carbenes. Herein, we demonstrate the important role of unique σ0π2 carbenes in the 1,1-hydroboration and bis-carbene functionalization of N2 using density functional theory calculations.

Activation of dinitrogen (N2) under mild conditions has been a particularly challenging project for decades, owing to the highly strong N≡N triple bond. In recent years, the main group species have emerged as a prominent strategy in the field of dinitrogen activation, but the reported examples remain particularly rare compared with transition metal complexes. Herein, we performed a comprehensive density functional theory (DFT) calculation of N2 activation by boron radical cations.

Although main group species have emerged in the field of dinitrogen activation in recent years, the reported examples are particularly rare in comparison with transition metal complexes due to their significant challenges. Herein, we demonstrate a [4 + 2] cycloaddition reaction of N2 (with an activation energy as low as 12.5 kcal mol–1) initiated by an inorganic benzene via density functional theory calculations. Such N2 activation is supported by the elongated nitrogen–nitrogen bond distance (dNN), decreased vibration frequency (νNN), and weakened Wiberg bond index (WBINN).

Although the main group species in the s and p blocks have begun to gain prominence in the field of dinitrogen (N2) activation in recent years, reports of carbene-mediated N2 activation remain particularly rare, especially for carbenes with a σ0π2 electronic configuration. Herein, we demonstrate examples of N2 activation initiated by a carbene with a σ0π2 electronic configuration and consequent N2 hydroboration reaction (with a reaction barrier as low as 19.9 kcal/mol) via density functional theory calculations.

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.

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 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.