Acid-Promoted Selective Carbon–Fluorine Bond Activation and Functionalization of Hexafluoropropene by Nickel Complexes Supported with Phosphine Ligands
收藏NIAID Data Ecosystem2026-03-08 收录
下载链接：
https://figshare.com/articles/dataset/Acid_Promoted_Selective_Carbon_Fluorine_Bond_Activation_and_Functionalization_of_Hexafluoropropene_by_Nickel_Complexes_Supported_with_Phosphine_Ligands/2345446
下载链接
链接失效反馈官方服务：
资源简介：
The
electron-rich complex Ni(PMe3)4 was utilized
to react with perfluoropropene to obtain Ni(CF2CFCF3)(PMe3)3 (1). The selective
C–F bond activation process of the π-coordinated perfluoropropene
in 1 was conducted with the promotion of Lewis acids
(ZnCl2, LiBr, and LiI) under mild conditions to afford
the products Ni(CF3CCF2)(PMe3)2X (X = Cl (2), Br (3), I (4)). The structures of complexes 2 and 3 determined by X-ray single-crystal diffraction confirmed
that the C–F bond activation occurred at the geminal position
of the trifluoromethyl group. Surprisingly, CF3COOH as
a protonic acid could also carry out a similar activation reaction
to give rise to Ni(CF3CCF2)(CF3COO)(PMe3)2 (7), while only the
addition products Ni(CF2CFHCF3)(CH3COO)(PMe3) (5) and Ni(CF2CFHCF3)(CH3SO3)(PMe3) (6) were obtained with CH3COOH and CH3SO3H. The transmetalation products Ni(CF3CCF2)Ph(PMe3)2 (8), Ni(CF3CCF2)(p-MeOPh)(PMe3)2 (9), and Ni(CF3CCF2)(CCPh)(PMe3)2 (10) were obtained through the reactions of Ni(CF3CCF2)(PMe3)2Cl (2) with PhMgBr,
(p-MeOPh)MgBr, and PhCCLi. In contrast, the
reaction of complex 2 with PhCH2CH2MgBr delivered complex 11, Ni(CF3CHC–CH2CH2Ph)(PMe3)2, via double
C–F bond activation. All of the C(sp2)–F
bonds in complex 11 were activated and cleaved. The structures
of complexes 5 and 7–11 were determined by X-ray single-crystal structure analysis. A reasonable
mechanism was proposed and partially experimentally verified through
operando IR and in situ 1H NMR spectroscopy.
创建时间：
2013-12-09
