American Chemical Society
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Norcaradiene–Cycloheptatriene Equilibrium: A Heavy-Atom Quantum Tunneling Case

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journal contribution
posted on 2024-06-18, 14:11 authored by Juan García de la Concepción, José C. Corchado, Pedro Cintas, Reyes Babiano
The equilibrium between norcaradiene and cycloheptatriene, which has captivated chemists for more than half a century, is revisited by state-of-the-art quantum chemical calculations. Our theoretical data significantly deviate from the experimental results (J. Am. Chem. Soc., 1981, 26, 7791–7792), especially at low temperatures, where isomerization is dominated by heavy-atom tunneling. This effect results in an extremely short half-life for norcaradiene, rendering it undetectable. This work sheds light on this equilibrium, updating the kinetic and thermodynamic data while also expanding the repertoire of organic reactions controlled by this exotic quantum effect.