Photochemistry and Reactivity of the Phenyl Radical–Water System: A Matrix Isolation and Computational Study |
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Authors: | Artur Mardyukov Rachel Crespo‐Otero Dr. Elsa Sanchez‐Garcia Dr. Wolfram Sander Prof. Dr. |
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Affiliation: | 1. Lehrstuhl für Organische Chemie II, Ruhr‐Universit?t Bochum, 44780 Bochum (Germany), Fax: (+49)?234‐321‐4353;2. Max‐Planck Institut für Kohlenforschung, Mülheim an der Ruhr, Kaiser‐Wilhelm‐Platz 1, 45470 Mülheim an der Ruhr (Germany) |
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Abstract: | The reaction of the phenyl radical 1 with water has been investigated by using matrix isolation spectroscopy and quantum chemical calculations. The primary thermal product of the reaction between 1 and water is a weakly bound complex stabilized by an OH???π interaction. This complex is photolabile, and visible‐light irradiation (λ>420 nm) results in hydrogen atom transfer from water to radical 1 and the formation of a highly labile complex between benzene and the OH radical. This complex is stable under the conditions of matrix isolation, however, continuous irradiation with λ>420 nm light results in the complete destruction of the aromatic system and formation of an acylic unsaturated ketene. The mechanisms of all reaction steps are discussed in the light of ab initio and DFT calculations. |
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Keywords: | density functional calculations infrared spectroscopy matrix isolation photochemistry radical reactions |
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