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Issue 29, 2017
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A three-state model for the photo-Fries rearrangement

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Abstract

A three-state model for the photo-Fries rearrangement (PFR) is proposed based on multiconfigurational calculations. It provides a comprehensive mechanistic picture of all steps of the reaction, from the photoabsorption to the final tautomerization. The three states participating in the PFR are an aromatic 1ππ*, which absorbs the radiation; a pre-dissociative 1nπ*, which transfers the energy to the dissociative region; and a 1πσ*, along which dissociation occurs. The transfer from 1ππ* to 1nπ* involves pyramidalization of the carbonyl carbon, while transfer from 1nπ* to 1πσ* takes place through CO stretching. Different products are available after a conical intersection with the ground state. Among them is a recombined radical intermediate, which can yield ortho-PFR products after an intramolecular 1,3-H tunneling. The three-state model is developed for phenyl acetate, the basic prototype for the PFR, and it reconciles the theory with a series of observations from time-resolved spectroscopy. It also delivers a rational way to optimize PFR yields, since, as shown for four different systems, diverse substituents can change the energetic order of the 1ππ* and 1nπ* states, preventing or enhancing the PFR.

Graphical abstract: A three-state model for the photo-Fries rearrangement

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Publication details

The article was received on 05 Jun 2017, accepted on 30 Jun 2017 and first published on 03 Jul 2017


Article type: Paper
DOI: 10.1039/C7CP03777E
Citation: Phys. Chem. Chem. Phys., 2017,19, 19103-19108
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    A three-state model for the photo-Fries rearrangement

    J. M. Toldo, M. Barbatti and P. F. B. Gonçalves, Phys. Chem. Chem. Phys., 2017, 19, 19103
    DOI: 10.1039/C7CP03777E

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