title: Computational study with DFT and kinetic models on the mechanism of photoinitiated aromatic perfluoroalkylations.
abstract: A combination of DFT calculations and kinetic models is applied to fully elucidate the seemingly complex reactivity of α-cyano arylacetates toward metal-free photoinitiated aromatic perfluoroalkylation. The resulting mechanistic framework rationalizes the observed quantum yield as well as the differences in reactivity and/or selectivity of seemingly similar substrates. The use of a kinetic model for the chemical interpretation of the DFT-computed reaction constants is shown to be critical.
authors.affiliation: †Institute of Chemical Research of Catalonia (ICIQ), Avgda. Països Catalans 16, 43007 Tarragona, Catalonia, Spain.
authors.forename: Victor M
authors.initials: VM
authors.lastname: Fernández-Alvarez
authors.affiliation: †Institute of Chemical Research of Catalonia (ICIQ), Avgda. Països Catalans 16, 43007 Tarragona, Catalonia, Spain.
authors.forename: Manuel
authors.initials: M
authors.lastname: Nappi
authors.affiliation: †Institute of Chemical Research of Catalonia (ICIQ), Avgda. Països Catalans 16, 43007 Tarragona, Catalonia, Spain.|‡Institució Catalana de Recerca i Estudis Avançats, Passeig Lluís Companys 23, 08010 Barcelona, Spain.
authors.forename: Paolo
authors.initials: P
authors.lastname: Melchiorre
authors.affiliation: †Institute of Chemical Research of Catalonia (ICIQ), Avgda. Països Catalans 16, 43007 Tarragona, Catalonia, Spain.|§Departament de Química,Universitat Autònoma de Barcelona, 08193 Bellaterra, Catalonia, Spain.
authors.forename: Feliu
authors.initials: F
authors.lastname: Maseras