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Aryl-CF3 coupling from phosphinoferrocene-ligated palladium(II) complexes
journal contribution
posted on 2023-05-20, 00:16 authored by Ferguson, DM, Bour, JR, Allan CantyAllan Canty, Kampf, JW, Sanford, MSThis 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).
History
Publication title
OrganometallicsVolume
38Pagination
519-526ISSN
0276-7333Department/School
School of Natural SciencesPublisher
Amer Chemical SocPlace of publication
1155 16Th St, Nw, Washington, USA, Dc, 20036Rights statement
Copyright 2019 American Chemical SocietyRepository Status
- Restricted