Heterogeneous Photoinduced Homolytic Aromatic Substitution of Electron-Rich Arenes with Perfluoroalkyl Groups in Water and Aqueous Media ? A Radical-Ion Reaction

The photoinduced electron transfer (PET) substitution reaction of electron-rich aromatic nuclei with perfluoroalkyl Rf groups was carried out in water or aqueous mixtures to render substitution products resulting from replacement of aromatic H atoms with the Rf moiety in good yields (57–88 %). Some...

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Detalles Bibliográficos
Autores: Barata Vallejo, Sebastian, Martín Flesia, Marina Aneley, Lantaño, Beatriz, Argüello, Juan Elias, Peñeñory, Alicia Beatriz, Postigo, Jose Alberto
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2013
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/16646
Acceso en línea:http://hdl.handle.net/11336/16646
Access Level:acceso abierto
Palabra clave:Heterogeneous Catalysis
Radical Reactions
Electron Transfer
Alkylation
Green Chemistry
Radical Ions
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
Descripción
Sumario:The photoinduced electron transfer (PET) substitution reaction of electron-rich aromatic nuclei with perfluoroalkyl Rf groups was carried out in water or aqueous mixtures to render substitution products resulting from replacement of aromatic H atoms with the Rf moiety in good yields (57–88 %). Some mechanistic aspects are discussed, supporting the notion of a PET reaction leading to a classical radical homolytic aromatic substitution (HAS) followed by an electron transfer (ET) and then a proton transfer (PT) sequence. A radical mechanism superimposed on a redox process is proposed to account for product formation. Evidence for the radical cation species (as an initiation event) generated from electron-rich arenes in the presence of perfluoroalkyl halides is provided by the UV/Vis transient spectra obtained by Nanosecond Laser Flash Photolysis techniques.