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

Ferguson, DM, Bour, JR, Canty, AJ, Kampf, JW and Sanford, MS 2019 , 'Aryl-CF3 coupling from phosphinoferrocene-ligated palladium(II) complexes' , Organometallics, vol. 38, no. 2 , pp. 519-526 , doi: 10.1021/acs.organomet.8b00828.

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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

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