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Understanding the C−F Bond Activation Mediated by Frustrated Lewis Pairs: Crucial Role of Non‐covalent Interactions
Author(s) -
CabreraTrujillo Jorge Juan,
Fernández Israel
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202004733
Subject(s) - hypervalent molecule , frustrated lewis pair , covalent bond , chemistry , lewis acids and bases , computational chemistry , density functional theory , atom (system on chip) , intermolecular force , stereochemistry , combinatorial chemistry , molecule , catalysis , organic chemistry , computer science , reagent , embedded system
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.