As a fundamental chemical property, aromaticity guides the synthesis of novel structures and materials. Replacing the carbon moieties of aromatic hydrocarbons with transition metal fragments is a promising strategy to synthesize intriguing organometallic counterparts with a similar aromaticity to their organic parents. However, since antiaromaticity will endow compound instability, it is a great challenge to obtain an antiaromatic organometallic counterpart based on such transition metal replacement in aromatic hydrocarbons.

Disilene has attracted considerable interests due to the trans-bending geometry which is significantly different from the planar alkene. However, the equilibrium between disilene and isomeric silylsilylene has not been fully understood. Here, we report a density functional theory (DFT) study on this equilibrium. Calculations reveal significant effects of substituent, aromaticity and base. Specifically, the parent disilene is thermodynamically more stable than the isomeric silylene.

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.

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.

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.