Quantum chemical calculations are reported for the thermal dimerizations of 1,3-cyclohexadiene at 1 atm and high pressures up to the GPa range. Computed activation enthalpies of plausible dimerization pathways at 1 atm agree well with the experiment activation energies and the values from previous calculations. High-pressure reaction profiles, computed by the recently developed extreme pressure-polarizable continuum model (XP-PCM), show that the reduction of reaction barrier is more profound in concerted reactions than in stepwise reactions, which is rationalized on the basis of the volume profiles of different mechanisms. A clear shift of the transition state towards the reactant under pressure is revealed for the [6+4]-ene reaction by the calculations. The computed activation volumes by XP-PCM agree excellently with the experimental values, confirming the existence of competing mechanisms in the thermal dimerization of 1,3-cyclohexadiene.

High-Pressure Reaction Profiles and Activation Volumes of 1,3-Cyclohexadiene Dimerizations Computed by the Extreme Pressure-Polarizable Continuum Model (XP-PCM) / Chen, B.; Houk, K. N.; Cammi, R.. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - (2022), p. e202200246. [10.1002/chem.202200246]

High-Pressure Reaction Profiles and Activation Volumes of 1,3-Cyclohexadiene Dimerizations Computed by the Extreme Pressure-Polarizable Continuum Model (XP-PCM)

Cammi R.
2022-01-01

Abstract

Quantum chemical calculations are reported for the thermal dimerizations of 1,3-cyclohexadiene at 1 atm and high pressures up to the GPa range. Computed activation enthalpies of plausible dimerization pathways at 1 atm agree well with the experiment activation energies and the values from previous calculations. High-pressure reaction profiles, computed by the recently developed extreme pressure-polarizable continuum model (XP-PCM), show that the reduction of reaction barrier is more profound in concerted reactions than in stepwise reactions, which is rationalized on the basis of the volume profiles of different mechanisms. A clear shift of the transition state towards the reactant under pressure is revealed for the [6+4]-ene reaction by the calculations. The computed activation volumes by XP-PCM agree excellently with the experimental values, confirming the existence of competing mechanisms in the thermal dimerization of 1,3-cyclohexadiene.
2022
High-Pressure Reaction Profiles and Activation Volumes of 1,3-Cyclohexadiene Dimerizations Computed by the Extreme Pressure-Polarizable Continuum Model (XP-PCM) / Chen, B.; Houk, K. N.; Cammi, R.. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - (2022), p. e202200246. [10.1002/chem.202200246]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2922468
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