Quantum Tunneling Instability in Pericyclic Reactions: The Cheletropic, Coarctate, and Ene Cases.

Some retro-pericyclic reactions, as a result of their high exothermicity and short trajectories, are the perfect ground for heavy atom tunneling molecular decompositions, also known as "quantum tunneling instability" (QTI). Considering this effect, in our first installment [Frenklach, A.; Amlani, H.; Kozuch, S. Quantum Tunneling Instability in Pericyclic Reactions. J. Am. Chem. Soc. 2024, 146 (17), 11823-11834, DOI: 10.1021/jacs.4c00608], we computed several retro-Diels-Alder reactions, predicting that many studied reactants cannot be isolated. Herein, we will explore the QTI of retro-cheletropic, coarctate, and ene exemplars, where again we hypothesize the impossibility to detect their reactants.

Quantum Tunneling Instability in Pericyclic Reactions.

Several cycloreversion reactions of the retro-Diels-Alder type were computationally assessed to understand their quantum tunneling (QT) reactivity. N2, CO, and other leaving groups were considered based on their strong exothermicity, as it reduces their thermodynamic and kinetic stabilities. Our results indicate that for many of these reactions, it is essential to take into account their QT decomposition rate, which can massively weaken their molecular stability and shorten their half-lives even at deep cryogenic temperatures. In practical terms, this indicates that many supposedly stable molecules will actually be unsynthesizable or unisolable, and therefore trying to prepare or detect them would be a futile attempt. In addition, we discuss the importance of tunneling to correctly understand the enthalpy of activation and the collective atomic effect on the tunneling kinetic isotope effects to test if third-row atoms can tunnel in a chemical reaction. This project raises the question of the importance of in silico chemistry to guide in vitro chemistry, especially in cases where the latter cannot solve its own uncertainties.

Coordination-Directed Growth of Transition-Metal-Crystalline-Carbon Composites with Controllable Metal Composition.

Transition-metal-carbon (CTM) composites show ample activity in many catalytic reactions. However, control of composition, distribution, and properties is challenging. Now, a straightforward path for the synthesis of transition-metal nanoparticles engulfed in crystalline carbon is presented with excellent control over the metal composition, amount, ratio, and catalytic properties. This approach uses molten monomers that coordinate metals ions at high temperature. At high temperatures, strong coordination bonds direct the growth of carbon material with homogeneous metals distribution and with negligible losses, owing to the liquid-like reaction compared to the traditional solid-state reaction. The strength of the approach is demonstrated by the synthesis of mono, binary, and trinary transition-metal-crystalline-carbon composites with tunable and precise elemental composition as well as good electrochemical properties as oxygen evolution reaction electrocatalysts.