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...
| Authors: | , , , , , |
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| Format: | article |
| Status: | Published version |
| Publication Date: | 2013 |
| Country: | Argentina |
| Institution: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repository: | CONICET Digital (CONICET) |
| Language: | English |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/16646 |
| Online Access: | http://hdl.handle.net/11336/16646 |
| Access Level: | Open access |
| Keyword: | Heterogeneous Catalysis Radical Reactions Electron Transfer Alkylation Green Chemistry Radical Ions https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Summary: | 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. |
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