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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
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: | 33 |
| Deposited By: | Chemistry |
| Deposited On: | 2017-08-31 |
| Last Modified: | 2018-05-30 |
| Downloads: | 0 |
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