Activation of the strongest triplet bond in molecular nitrogen (N2) under mild conditions is particularly challenging. Recently, its fixation and reduction were achieved by highly reactive dicoordinated borylene species at ambient conditions, ripping the limits of harsh reaction conditions by metallic species. Less reactive species with a facile preparation could be desirable for next-generation N2 activation. Now density functional theory calculations reveal that tricoordinated boranes could be a potential candidate of N2 activation/functionalization.

Aromaticity is one of the most basic concepts in organic chemistry. The planar Möbius aromatic metallapentalynes and metallapentalenes have been attracted considerable attention in the past few years. However, the aromaticity of metallapentalenes containing heteroatoms (such as B, N, and O), termed as hetero‐metallapentalenes, is rarely studied. Here, we theoretically investigated the stability and aromaticity of a series of hetero‐metallapentalenes.

Molecular nitrogen (N2), an abundant component of the atmosphere, is appealing for industrial value‐added products. However, its intrinsic inertness limits its activation to mainly metallic species. Environmental concerns and harsh reaction conditions have resulted in a demand for alternate nonmetallic and nontoxic routes to activate and functionalize N2 at ambient conditions. Comprehensive density functional theory (DFT) calculations are performed on N2 activation by boron species, specifically for the experimentally more accessible tricoordinated boron compounds.

Metallaaromatics have attracted considerable attention in recent years because they can display properties of both organic and organometallic species. However, it remains unclear whether Clar’s rule could be applied to organometallic chemistry despite its proposal in 1950s. Here, we investigate the relative stabilities of 49 organic and organometallic species by density functional theory (DFT) calculations.

Pentafulvenes are dipolar hydrocarbons since they shift their π-electrons to achieve Hückel aromaticity and thus the electron donating groups at the exocyclic position can enhance their aromaticity. Silapentafulvenes are analogues of pentafulvene formed by the replacement of the carbon atoms at the exocyclic CC double bond with a silicon atom in pentafulvene. It remains unclear how the aromaticity of 5-silapentafulvenes and 6-silapentafulvenes can be changed due to the polarization of the CSi double bond.

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.

Olefin metathesis is a fundamental organic reaction of great importance that led to the 2005 Nobel Prize in Chemistry. As a variation of olefin–olefin metathesis, carbonyl–olefin metathesis (COM) is less developed, but still significant progress has been made recently. However, how the aromaticity affects the reaction mechanisms remains unclear. Here we perform density functional theory calculations on iron(III) catalyzed COM in 2,5- and 3,5-hexadienals.

Pincer complexes are a remarkably versatile family benefited from their stability, diversity, and tunability. Many of them contain aromatic organic rings at the periphery, and aromaticity plays an important role in their stability and properties, whereas their metallacyclic cores are not aromatic. Herein, we report rhodapentalenes, which can be viewed as pincer complexes in which the metallacyclic cores exhibit considerable aromatic character. Rhodapentalenes show good thermal stability, although the rhodium-carbon bonds in such compounds are fragile.

Unusual 1,2‐migration reactions of N‐heterocyclic carbene (NHC) on transition metals were investigated using density functional theory calculations. Our results reveal that the electronic properties, ring strain of the four‐membered ring, and aromaticity of NHC play crucial roles in the thermodynamics of such a 1,2‐migration.

The [1,5]‐migration reaction has attracted considerable attention from experimentalists and theoreticians for decades. Although it has been extensively investigated in various systems, studies on pyrrolium derivatives are underdeveloped. Herein, a theoretical study on the reaction mechanism of [1,5]‐migration in both pyrrolium and pyrrole derivatives is presented.