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Сan Plasmon Change Reaction Path? An Unprecedented Regioselective Decomposition of Unsymmetrical Iodonium Salts

preprint
submitted on 11.04.2020 and posted on 13.04.2020 by Elena Miliutina, Olga Guselnikova, Natalia Soldatova, Polina Bainova, Roman Elashnikov, Přemysl Fitl, Theo Kurten, Mekhman Yusubov, Václav Švorčík, Rashid R. Valiev, Mohamed Chehimi, Oleksiy Lyutakov, Pavel Postnikov

Plasmon-assisted transformations of organic compounds represent a novel opportunity for conversion of light to chemical energy at room temperature. Herein, we propose a comprehensive investigation of plasmon-triggered decomposition of iodonium salts containing various substituents (ISs). We found that plasmon interaction with unsymmetrical ISs led to the intramolecular excitation of electron followed by the regioselective cleavage of C–I bond with the formation of electron-rich radical species. Such unprecedented C–I cleavage brings the possibility of selective surface modification using ISs. The high regioselectivity is explained by the direct excitation of electron to LUMO with the formation of dissociative excited state ac-cording to quantum-chemical modeling.

Funding

Russian Science Foundation (17-73-20066)

GACR (19-24603Y)

History

Email Address of Submitting Author

postnikov@tpu.ru

Institution

Tomsk Polytechnic University

Country

Russia

ORCID For Submitting Author

0000-0001-9713-1290

Declaration of Conflict of Interest

No conflict of interest

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