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Establishing the Role of Triflate Anions in H(2) Activation by a Cationic Triorganotin(IV) Lewis Acid

[Image: see text] Cationic Lewis acids (LAs) are gaining interest as targets for frustrated Lewis pair (FLP)-mediated catalysis. Unlike neutral boranes, which are the most prevalent LAs for FLP hydrogenations, the Lewis acidity of cations can be tuned through modulation of the counteranion; however,...

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Detalles Bibliográficos
Autores principales: Sapsford, Joshua S., Csókás, Dániel, Scott, Daniel J., Turnell-Ritson, Roland C., Piascik, Adam D., Pápai, Imre, Ashley, Andrew E.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7469243/
https://www.ncbi.nlm.nih.gov/pubmed/32905389
http://dx.doi.org/10.1021/acscatal.0c02023
Descripción
Sumario:[Image: see text] Cationic Lewis acids (LAs) are gaining interest as targets for frustrated Lewis pair (FLP)-mediated catalysis. Unlike neutral boranes, which are the most prevalent LAs for FLP hydrogenations, the Lewis acidity of cations can be tuned through modulation of the counteranion; however, detailed studies on such anion effects are currently lacking in the literature. Herein, we present experimental and computational studies which probe the mechanism of H(2) activation using iPr(3)SnOTf (1-OTf) in conjunction with a coordinating (quinuclidine; qui) and noncoordinating (2,4,6-collidine; col) base and compare its reactivity with {iPr(3)Sn·base}{Al[OC(CF(3))(3)](4)} (base = qui/col) systems which lack a coordinating anion to investigate the active species responsible for H(2) activation and hence resolve any mechanistic roles for OTf(–) in the iPr(3)SnOTf-mediated pathway.