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Stoichiometric and catalytic aryl-perfluoroalkyl coupling at tri-tert-butylphosphine palladium(II) complexes

Citation

Ferguson, DM and Bour, JR and Canty, AJ and Kampf, JW and Sanford, MS, Stoichiometric and catalytic aryl-perfluoroalkyl coupling at tri-tert-butylphosphine palladium(II) complexes, Journal of the American Chemical Society, 139, (34) pp. 11662-11665. ISSN 0002-7863 (2017) [Refereed Article]

Copyright Statement

Copyright 2017 American Chemical Society

DOI: doi:10.1021/jacs.7b05216

Abstract

This Communication describes studies of Ph–RF (RF = CF3 or CF2CF3) coupling at Pd complexes of general structure (PtBu3)PdII(Ph)(RF). The CF3 analogue participates in fast Ph-CF3 coupling (<5 min at 80 °C). However, the formation of side products limits the yield of this transformation as well as its translation to catalysis. DFT and experimental studies suggest that the side products derive from facile α-fluoride elimination at the 3-coordinate PdII complex. Furthermore, they show that this undesired pathway can be circumvented by changing from a CF3 to a CF2CF3 ligand. Ultimately, the insights gained from stoichiometric studies enabled the identification of Pd(PtBu3)2 as a catalyst for the Pd-catalyzed cross-coupling of aryl bromides with TMSCF2CF3 to afford pentafluoroethylated arenes.

Item Details

Item Type:Refereed Article
Keywords:catalysis, palladium, fluorocarbon, DFT
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Organometallic chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Canty, AJ (Professor Allan Canty)
ID Code:120824
Year Published:2017
Web of Science® Times Cited:42
Deposited By:Chemistry
Deposited On:2017-08-31
Last Modified:2022-08-22
Downloads:0

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