Understanding the C−F Bond Activation Mediated by Frustrated Lewis Pairs: Crucial Role of Non-covalent Interactions
Jorge Juan Cabrera-Trujillo
Departamento de Química Orgánica I and, Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
Search for more papers by this authorCorresponding Author
Prof. Dr. Israel Fernández
Departamento de Química Orgánica I and, Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
Search for more papers by this authorJorge Juan Cabrera-Trujillo
Departamento de Química Orgánica I and, Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
Search for more papers by this authorCorresponding Author
Prof. Dr. Israel Fernández
Departamento de Química Orgánica I and, Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
Search for more papers by this authorGraphical Abstract
C−F activation: The activation of single C−F bonds in di- and trifluoromethyl groups mediated by frustrated Lewis pairs (FLPs) exhibits a peculiar cooperative action, which is markedly different from related FLP-mediated processes, and where non-covalent interactions established between the Lewis base and the substrate play a decisive role.
Abstract
The activation of a single C−F bond in di- and trifluoromethyl groups by frustrated Lewis pairs (FLPs) has been computationally explored by means of Density Functional Theory calculations. It is found that in this activation reaction the FLP partners exhibit a peculiar cooperative action, which is markedly different from related FLP-mediated processes, and where non-covalent interactions established between the Lewis base and the substrate play a decisive role. In addition, the process proceeds through the intermediacy of a hypervalent species featuring a pentacoordinate carbon atom, which is rare in the chemistry of FLPs. The physical factors controlling this process as well as the bonding situation of these hypervalent intermediates have been quantitatively analyzed in detail by using state-of-the-art computational methods to not only rationalize the mechanism of the transformation but also to guide experimentalists towards the realization of these so far elusive hypervalent systems.
Conflict of interest
The authors declare no conflict of interest.
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