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Single‐Electron Transfer in Frustrated Lewis Pair Chemistry
Author(s) -
Holtrop Flip,
Jupp Andrew R.,
Kooij Bastiaan J.,
Leest Nicolaas P.,
Bruin Bas,
Slootweg J. Chris
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202009717
Subject(s) - lewis acids and bases , frustrated lewis pair , chemistry , adduct , electron transfer , hydride , radical , substrate (aquarium) , molecule , radical ion , computational chemistry , stereochemistry , photochemistry , organic chemistry , catalysis , ion , hydrogen , oceanography , geology
Frustrated Lewis pairs (FLPs) are well known for their ability to activate small molecules. Recent reports of radical formation within such systems indicate single‐electron transfer (SET) could play an important role in their chemistry. Herein, we investigate radical formation upon reacting FLP systems with dihydrogen, triphenyltin hydride, or tetrachloro‐1,4‐benzoquinone (TCQ) both experimentally and computationally to determine the nature of the single‐electron transfer (SET) events; that is, being direct SET to B(C 6 F 5 ) 3 or not. The reactions of H 2 and Ph 3 SnH with archetypal P/B FLP systems do not proceed via a radical mechanism. In contrast, reaction with TCQ proceeds via SET, which is only feasible by Lewis acid coordination to the substrate. Furthermore, SET from the Lewis base to the Lewis acid–substrate adduct may be prevalent in other reported examples of radical FLP chemistry, which provides important design principles for radical main‐group chemistry.