title: Imine-assisted C-F bond activation using low-valent cobalt compounds supported by trimethylphosphine ligands and formation of novel organic fluorides.
abstract: A cyclometalation reaction involving C-F bond activation at a cobalt(i) center with an aldazine-N atom as anchoring group affords ortho-chelated cobalt(iii) complexes containing a [C-Co-F] fragment [CoFMe(PMe(3))(2){(C(6)H(3)F-ortho)CH[double bond, length as m-dash]N-R}] 5-8. Under similar reaction conditions π-coordinated cobalt(0) complexes [Co(PMe(3))(3)((C(6)H(3)F-ortho)CH[double bond, length as m-dash]N-R)] 12-14 were formed when [Co(PMe(3))(4)], instead of [CoMe(PMe(3))(4)], was applied. C-F bond activation did not occur. Carbonylation of complexes 6-8 delivered novel organic fluorides 15-17. A proposed formation mechanism of the novel organic fluorides with demetallation and carbonylation of complexes 6-8 by CO is discussed with experimental support. As important intermediates, an acetyl cobalt complex, [CoFMeC[double bond, length as m-dash]O(PMe(3))(2){(C(6)H(3)F-ortho)CH[double bond, length as m-dash]N-R}] 20, and a 19-electron cobalt(0) complex, Co(CO)(3)(PMe(3))(2)21, were structurally characterized. The crystal and molecular structures of complexes 5, 6, 8, 12, 20 and 21 were determined by X-ray diffraction.
authors.affiliation: School of Chemistry and Chemical Engineering, Shandong University, Shanda Nanlu 27, 250100, Jinan, People's Republic of China. xli63@sdu.edu.cn.
authors.forename: Zhe
authors.initials: Z
authors.lastname: Lian
authors.forename: Xiaofeng
authors.initials: X
authors.lastname: Xu
authors.forename: Hongjian
authors.initials: H
authors.lastname: Sun
authors.forename: Yue
authors.initials: Y
authors.lastname: Chen
authors.forename: Tingting
authors.initials: T
authors.lastname: Zheng
authors.forename: Xiaoyan
authors.initials: X
authors.lastname: Li