As an electron-rich species, radical anions have a wide range of applications in organic synthesis. In addition, aromaticity is an essential concept in chemistry that has attracted considerable attention from experimentalists and theoreticians. However, it remains unknown whether there is a relationship between aromaticity and thermodynamic stability of a radical anion. In this work, we demonstrate that the thermodynamically stable radical anions could be formed by the corresponding antiaromatic neutral species through density functional theory calculations.

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.

Activation of dinitrogen (N2, 78%) and dioxygen (O2, 21%) has fascinated chemists and biochemists for decades. The industrial conversion of N2 to ammonia requires extremely high temperatures and pressure. Here we report the first example of N2 and O2 cleavage by a uranium complex, [N(CH2CH2NPiPr2)3U]2(TMEDA), under ambient conditions without an external reducing agent. The N2 triple bond breaking implies a U(III)-P(III) six-electron reduction. The hydrolysis of the N2 reduction product allows the formation of ammonia or nitrogen-containing organic compound.

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.

Frustrated Lewis pairs (FLPs) represent a new paradigm of main‐group chemistry. The Lewis acidic centers in FLP chemistry are typically B and Al atoms in the studies reported over the past decade, and most of them are tri‐coordinated with strong electron‐withdrawing groups. Herein, we report a Ga/P system containing an unprecedented four‐coordinated Lewis acidic Ga center. This Ga/P species performs classical addition reactions toward heterocumulenes, alkyne, diazomethane, and transition metal complex. Regioselective formation of the products can be rationalized by DFT calculations.

Aromaticity, one of the central topics in chemistry, has attracted continuing interest of both experimentalists and theoreticians.

Two newly discovered linear compounds tetraboronate and boroxine stabilized by digermylene are reported, which feature a B4O5 chain and a B3O3 ring, respectively. DFT calculations reveal that not only can digermylene stabilize the electron-deficient boron centers, but also increase the energies of the LUMOs of the boron moiety. Our results provide a hint for the development of boronate covalent organic frameworks.