标题：Preparation of organocobalt complexes through C-F/C-H bond activation of polyfluoroaryl imines
作者：Lu, Faguan; Sun, Hongjian; Wang, Lin; Li, Xiaoyan
作者机构：[Lu, Faguan; Sun, Hongjian; Wang, Lin; Li, Xiaoyan] Shandong Univ, Sch Chem & Chem Engn, Key Lab Special Funct Aggregated Mat, Minist Educ, Jinan 2501 更多
通讯作者地址：[Li, XY]Shandong Univ, Sch Chem & Chem Engn, Key Lab Special Funct Aggregated Mat, Minist Educ, Shanda Nanlu 27, Jinan 250199, Peoples R China.
来源：INORGANIC CHEMISTRY COMMUNICATIONS
关键词：C - H activation; C - F activation; Cobalt complex; C,C-coupling;; Trimethylphosphine
摘要：In this paper, we reported the C-F and C-H bond activation of polyfluoroimine ligands induced by CoMe(PMe3)(4). The reaction of pentafluorophenylmethylidene-2,6-diisopropylaniline 1 with CoMe(PMe3)(4) afforded an ortho-chelated cobalt(l) complex [Co(PMe3)(3)(C6F4-ortho-CH = N-C6H3(iso-Pr)(2(ortho, ortho)))] (5) via C-F bond activation and subsequent elimination of methyl fluoride. Under similar reaction conditions, the reactions of polyfluoroarylimines 2-4 with come(PMe3)(4) afforded the penta-coordinate cobalt(l) complexes 6-8 via C-H bond activation and subsequent elimination of methane [Co(PMe3)(3)(C6H2F2(meta, meta)-ortho-(CH = N-C6H4Clpara)] (6), [Co(PMe3)(3)(C6H2F2(meta, para)-ortho-(CH = N-C6H4Clpara)] (7), and [Co(PMe3)(3)(C6H3(meta, meta, para)-ortho-(CH = N-C6H4Clpara)] (8). Complexes 5-8 were characterized through IR, H-1 NMR, P-31 NMR, F-19 NMR and elemental analyses. The crystal and molecular structures of complexes 5, 6 and 8 were determined by X-ray single crystal diffraction. The reactions of 8 with Mel and EtBr afforded organic fluorides 9-10. A proposed formation mechanism of 9-10 with the oxidative addition of RX at the cobalt(I) center of 8 and reductive elimination via CC-coupling was discussed. (C) 2014 Elsevier B.V. All rights reserved.