摘要
In this paper the C--F bond activation of polyfluoroaryl imines is explored at cobalt(0) center with an imine-N atom as an anchoring group. The reaction of F5C6-CH=N-(2'-ClC6H4) (2) and FsC6-CH=N-C6H5 (3) with Co(PMe3h afforded the C-F bond activation products (ortho-F4C6-CH=N-(2'-CIC6H4))Co(I)(PMe3)3 (5) and (ortho-F4C6-CH=N-C6Hs)Co(II)(F)(PMe3)2 (6), while only n-(C=N) coordinated cobalt(0) complex (2,4,5- F3C6H2-CH=N-(4'-ClC6H4))Co(0)(PMe3)3 (4) was obtained from 2,4,5-F3C6H2-CH=N-(4'-C1C6H4) (1) without C--F bond activation. Complexes 4--6 were characterized through X-ray single crystal diffraction. It was also found that dialkylation of N-(perfluorobenzylidene)benzenamine with organozinc reagents could be catalyzed by Co(PMe3)4 via C,C-coupling reaction under mild conditions.
In this paper the C--F bond activation of polyfluoroaryl imines is explored at cobalt(0) center with an imine-N atom as an anchoring group. The reaction of F5C6-CH=N-(2'-ClC6H4) (2) and FsC6-CH=N-C6H5 (3) with Co(PMe3h afforded the C-F bond activation products (ortho-F4C6-CH=N-(2'-CIC6H4))Co(I)(PMe3)3 (5) and (ortho-F4C6-CH=N-C6Hs)Co(II)(F)(PMe3)2 (6), while only n-(C=N) coordinated cobalt(0) complex (2,4,5- F3C6H2-CH=N-(4'-ClC6H4))Co(0)(PMe3)3 (4) was obtained from 2,4,5-F3C6H2-CH=N-(4'-C1C6H4) (1) without C--F bond activation. Complexes 4--6 were characterized through X-ray single crystal diffraction. It was also found that dialkylation of N-(perfluorobenzylidene)benzenamine with organozinc reagents could be catalyzed by Co(PMe3)4 via C,C-coupling reaction under mild conditions.
基金
Acknowledgement We gratefully acknowledge the support by National Natural Science Foundation of China (No. 21172132). We also thank the kind assistance from Prof. Dieter Fenske and Dr. Olaf Fuhr (Karlsruhe Nano-Micro Facility, KNMF) for the X-ray diffraction analysis.