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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]


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DOI: doi:10.1021/jacs.7b05216

Abstract

This Communication describes studies of PhRF (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:Other Chemical Sciences
Research Field:Organometallic Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Canty, AJ (Professor Allan Canty)
ID Code:120824
Year Published:2017
Web of Science® Times Cited:4
Deposited By:Chemistry
Deposited On:2017-08-31
Last Modified:2018-03-26
Downloads:0

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