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Aryl-CF3 coupling from phosphinoferrocene-ligated palladium(II) complexes

Citation

Ferguson, DM and Bour, JR and Canty, AJ and Kampf, JW and Sanford, MS, Aryl-CF3 coupling from phosphinoferrocene-ligated palladium(II) complexes, Organometallics, 38, (2) pp. 519-526. ISSN 0276-7333 (2019) [Refereed Article]

Copyright Statement

Copyright 2019 American Chemical Society

DOI: doi:10.1021/acs.organomet.8b00828

Abstract

This article describes a detailed investigation of ligand effects on PhCF3 coupling from phosphinoferrocene-ligated PdII(Ph)(CF3) complexes. This study reveals that increasing the size of the phosphine substituents results in an enhanced rate of PhCF3 coupling, with (DtBPF)Pd(Ph)(CF3) (DtBPF = 1,1′-bis(di-tert-butylphosphino)ferrocene) being the most reactive complex. The mechanism of PhCF3 bond formation from both (DtBPF)Pd(Ph)(CF3) and (DiPrPF)Pd(Ph)(CF3) (DiPrPF = 1,1′-bis(diisopropylphosphino)ferrocene) was interrogated experimentally and computationally. These studies implicate a pathway involving concerted PhCF3 bond-forming reductive elimination from the four-coordinate PdII centers. An alternative pathway involving α-fluoride elimination and subsequent PhF2CF coupling from PdII(CF2Ph)(F) intermediates was also evaluated but was ruled out based on DFT as well as the independent synthesis and reactivity studies of (DiPrPF)Pd(CF2Ph)(F).

Item Details

Item Type:Refereed Article
Keywords:organopalladium, coupling reactions, DFT
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Transition Metal 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:130478
Year Published:2019
Web of Science® Times Cited:7
Deposited By:Chemistry
Deposited On:2019-01-29
Last Modified:2019-12-09
Downloads:0

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