Single-Electron Transfer in Frustrated Lewis Pair Chemistry.

Autor: Holtrop F; Van't Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD, Amsterdam, The Netherlands., Jupp AR; Van't Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD, Amsterdam, The Netherlands., Kooij BJ; Van't Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD, Amsterdam, The Netherlands., van Leest NP; Van't Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD, Amsterdam, The Netherlands., de Bruin B; Van't Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD, Amsterdam, The Netherlands., Slootweg JC; Van't Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD, Amsterdam, The Netherlands.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2020 Dec 01; Vol. 59 (49), pp. 22210-22216. Date of Electronic Publication: 2020 Oct 01.
DOI: 10.1002/anie.202009717
Abstrakt: 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.
(© 2020 The Authors. Published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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