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Photoinduced and Thermal Single‐Electron Transfer to Generate Radicals from Frustrated Lewis Pairs

Archetypal phosphine/borane frustrated Lewis pairs (FLPs) are famed for their ability to activate small molecules. The mechanism is generally believed to involve two‐electron processes. However, the detection of radical intermediates indicates that single‐electron transfer (SET) generating frustrate...

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Detalles Bibliográficos
Autores principales: Holtrop, Flip, Jupp, Andrew R., van Leest, Nicolaas P., Paradiz Dominguez, Maximilian, Williams, René M., Brouwer, Albert M., de Bruin, Bas, Ehlers, Andreas W., Slootweg, J. Chris
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7496419/
https://www.ncbi.nlm.nih.gov/pubmed/32259331
http://dx.doi.org/10.1002/chem.202001494
Descripción
Sumario:Archetypal phosphine/borane frustrated Lewis pairs (FLPs) are famed for their ability to activate small molecules. The mechanism is generally believed to involve two‐electron processes. However, the detection of radical intermediates indicates that single‐electron transfer (SET) generating frustrated radical pairs could also play an important role. These highly reactive radical species typically have significantly higher energy than the FLP, which prompted this investigation into their formation. Herein, we provide evidence that the classical phosphine/borane combinations PMes(3)/B(C(6)F(5))(3) and PtBu(3)/B(C(6)F(5))(3) both form an electron donor–acceptor (charge‐transfer) complex that undergoes visible‐light‐induced SET to form the corresponding highly reactive radical‐ion pairs. Subsequently, we show that by tuning the properties of the Lewis acid/base pair, the energy required for SET can be reduced to become thermally accessible.