Open Access Repository
Aryl-CF3 coupling from phosphinoferrocene-ligated palladium(II) complexes
Full text not available from this repository.
Abstract
This article describes a detailed investigation of ligand effects on Ph–CF3 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 Ph–CF3 coupling, with (DtBPF)Pd(Ph)(CF3) (DtBPF = 1,1′-bis(di-tert-butylphosphino)ferrocene) being the most reactive complex. The mechanism of Ph–CF3 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 Ph–CF3 bond-forming reductive elimination from the four-coordinate PdII centers. An alternative pathway involving α-fluoride elimination and subsequent PhF2C–F 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 Type: | Article |
---|---|
Authors/Creators: | Ferguson, DM and Bour, JR and Canty, AJ and Kampf, JW and Sanford, MS |
Keywords: | organopalladium, coupling reactions, DFT |
Journal or Publication Title: | Organometallics |
Publisher: | Amer Chemical Soc |
ISSN: | 0276-7333 |
DOI / ID Number: | 10.1021/acs.organomet.8b00828 |
Copyright Information: | Copyright 2019 American Chemical Society |
Related URLs: | |
Item Statistics: | View statistics for this item |
Actions (login required)
![]() |
Item Control Page |