reaction mechanism

Isotopic Oxygen Exchange between CeO2 and O2: A Heteroexchange Mechanism

Isotopic oxygen exchange (IOE) is a crucial reaction required in the purification of 238PuO2 which has been used as an important fuel in space exploration. Experimental studies on the IOE between 238PuO2 and O2 are costly and hazardous due to the radioactivity. With extremely similar crystal structures, CeO2 could be a fair surrogate for 238PuO2 in the investigation of physicochemical properties. Here, we perform density functional theory calculations to simulate the IOE between CeO2 and O2, wherein a heteroexchange mechanism is proposed.

Aromaticity‐promoted CO2 Capture by P/N‐Based Frustrated Lewis Pairs: A Theoretical Study

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.

Hyperconjugative aromaticity and protodeauration reactivity of polyaurated indoliums

Aromaticity generally describes a cyclic structure composed of sp2-hybridized carbon or hetero atoms with remarkable stability and unique reactivity. The doping of even one sp3-hybridized atom often damages the aromaticity due to the interrupted electron conjugation. Here we demonstrate the occurrence of an extended hyperconjugative aromaticity (EHA) in a metalated indole ring which contains two gem-diaurated tetrahedral carbon atoms. The EHA-involved penta-aurated indolium shows extended electron conjugation because of dual hyperconjugation.

Cu-Catalyzed Aromatic Metamorphosis of 3-Aminoindazoles

We present a novel Cu-catalyzed aromatic metamorphosis of 3-aminoindazoles via oxidative cleavage of two C–N bonds of 3-aminoindazoles. This unprecedented reactivity of 3-aminoindazoles allows one to forge diverse nitrile-containing triphenylenes in decent yields via generation of the cyano group in situ. The current study reveals that 3-aminoindazoles could be harnessed as radical precursors via oxidative denitrogenation, the reaction mechanism of which was supported by density functional theory calculations.

Reaction Mechanisms on Unusual 1,2‐Migrations of N‐Heterocyclic Carbene‐Ligated Transition Metal Complexes

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.

Aromaticity‐promoted C−F Bond Activation in Rhodium Complex: A Facile Tautomerization

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.

Mechanism of Nickel-Catalyzed Selective C–N Bond Activation in Suzuki-Miyaura Cross-Coupling of Amides: A Theoretical Investigation

In textbooks, the low reactivity of amides is attributed to the strong resonance stability. However, Garg and co-workers recently reported the Ni-catalyzed activation of robust amide C–N bonds, leading to conversions of amides into esters, ketones, and other amides with high selectivity. Among them, the Ni-catalyzed Suzuki-Miyaura coupling (SMC) of N-benzyl-N-tert-butoxycarbonyl (N-Bn-N-Boc) amides with pinacolatoboronate (PhBpin) was performed in the presence of K3PO4 and water. Water significantly enhanced the reaction.

Mechanism, catalysis and predictions of 1,3,2-diazaphospholenes: theoretical insight into highly polarized P–X bonds

Density functional theory (DFT) calculations were carried out to investigate the hydridic character of several main group hydrides. A P-hydrido-1,3,2-diazaphospholene 1f with two π-electron donor amino groups on the heterocyclic skeleton framework performs as a strong hydride donor owing to the significant n(N)–σ*(P–H) hyperconjugation. The natural bond orbital analysis reveals that high π-electron delocalization exists in both 1f and the corresponding stable phosphenium Ef+.

Probing the reactivity of microhydrated α-nucleophile in the anionic gas-phase SN2 reaction

To probe the kinetic performance of microsolvated α-nucleophile, the G2(+)M calculations were carried out for the gas-phase SN2 reactions of monohydrated and dihydrated α-oxy-nucleophiles XO−(H2O)n = 1,2 (X = HO, CH3O, F, Cl, Br), and α-sulfur-nucleophile, HSS−(H2O)n = 1,2, toward CH3Cl. We compared the reactivities of hydrated α-nucleophiles to those of hydrated normal nucleophiles.