Heterogeneous Photoinduced Electron Transfer Substitution of Electron-rich Aromatic Compounds with Perfluoroalkyl Groups in Water. A Radical-ion Chain Reaction.DOI: 10.1002/ ejoc.201201271

SEBASTIÁN BARATA-VALLEJO; MARINA MARTÍN FLESIA; JUAN E. ARGÜELLO; ALICIA B. PEÑÉÑORY; AL POSTIGO

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY

WILEY-V C H VERLAG GMBH

Lugar: Weinheim; Año: 2012

1434-193X

Abstract.The photoinduced electron transfer (PET) substitution reaction of electron rich aromatic nuclei with perfluoroalkyl Rf groups was carried out in wateror aqueous mixtures to render the substitution products resulting from replacement of aromatic H´s 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 proton transfer (PT) sequence.A radical mechanism superimposed with 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