Rehybridization dynamics into the pericyclic minimum of an electrocyclic reaction imaged in real-time

Autor: Y. Liu, D. M. Sanchez, M. R. Ware, E. G. Champenois, J. Yang, J. P. F. Nunes, A. Attar, M. Centurion, J. P. Cryan, R. Forbes, K. Hegazy, M. C. Hoffmann, F. Ji, M.-F. Lin, D. Luo, S. K. Saha, X. Shen, X. J. Wang, T. J. Martínez, T. J. A. Wolf
Rok vydání: 2023
Předmět:
Zdroj: Nature Communications. 14
ISSN: 2041-1723
Popis: Electrocyclic reactions are characterized by the concerted formation and cleavage of both {\sigma} and {\pi} bonds through a cyclic structure. This structure is known as a pericyclic transition state for thermal reactions and a pericyclic minimum in the excited state for photochemical reactions. However, the structure of the pericyclic geometry has yet to be observed experimentally. We use a combination of ultrafast electron diffraction and excited state wavepacket simulations to image structural dynamics through the pericyclic minimum of a photochemical electrocyclic ring-opening reaction in the molecule {\alpha}-terpinene. The structural motion into the pericyclic minimum is dominated by rehybridization of two carbon atoms, which is required for the transformation from two to three conjugated {\pi} bonds. The {\sigma} bond dissociation largely happens after internal conversion from the pericyclic minimum to the electronic ground state. These findings may be transferrable to electrocyclic reactions in general.
Comment: Combined manuscript and supplementary information
Databáze: OpenAIRE
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