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Computational Study with DFT and Kinetic Models on the Mechanism of Photoinitiated Aromatic Perfluoroalkylations
journal contribution
posted on 2015-06-05, 00:00 authored by Victor
M. Fernández-Alvarez, Manuel Nappi, Paolo Melchiorre, Feliu MaserasA 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.