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.

Fluorine is the most electronegative element in the periodic table. Thus, activation of the carbon–fluorine (C−F) bond, the strongest single bond to carbon, has attracted considerable interest from both experimentalists and theoreticians. In comparison with numerous approaches to activate C−F bonds, the aromaticity‐promoted method is less developed. Herein, we demonstrate that the C−F bond activation could be achieved by a facile tautomerization, benefitting from aromaticity, which can stabilize both the transition states and products.

Aromaticity, one of the most fundamental concepts in chemistry, has attracted considerable attention from both theoreticians and experimentalists. Much effort on aromaticity in organometallics has been devoted to metallabenzene and derivatives. In comparison, aromaticity in other organometallics is less developed. This Account describes how our group has performed quantum chemical calculations to examine aromaticity in recently synthesized novel organometallic complexes.

Molecular nitrogen (N2) is abundant in the atmosphere and nitrogen, found in many biomolecules, is an essential element of life. The Haber–Bosch process, developed over 100 years ago, requires relatively harsh conditions to activate N2 on the iron surface and generate ammonia for use as fertilizer or to produce other chemicals, leading to consumption of more than 2% of the world’s annual energy supply. Thus, developing approaches for N2 activation under mild conditions is particularly important and urgent.

Hyperconjugation and aromaticity are two of the most important concepts in chemistry. Mulliken and co‐workers combined both terms to explain the stability of cyclopentadiene. Here, we carried out DFT calculations on a series of mono‐ and disubstituted cyclopentadiene derivatives to investigate their hyperconjugative aromaticity. Our results revealed that one electropositive substituent can induce aromaticity, whereas one electronegative substituent prompts nonaromaticity rather than antiaromaticity.

Hyperconjugation, an interaction of electrons in a σ orbital or lone pair with an adjacent π or even σ antibonding orbital, can have a strong effect on aromaticity. However, most work on hyperconjugative aromaticity has been limited to main-group substituents. Here, we report a thorough density functional theory study to evaluate the aromaticity in various cyclopentadienes that contain both main-group and transition-metal substituents.

Besides its mathematical importance, the Möbius topology (twisted, single-sided strip) is intriguing at the molecular level, as it features structural elegance and distinct properties; however, it carries synthetic challenges. Although some Möbius-type molecules have been isolated by synthetic chemists accompanied by extensive computational studies, the design, preparation, and characterization of stable Möbius-conjugated molecules remain a nontrivial task to date, let alone that of molecular Möbius strips assembling into more complex topologies.