107607-99-8Relevant academic research and scientific papers
Preparation of hydrido [CNC]-pincer cobalt complexes via selective C-H/C-F bond activation and their catalytic performances
Yang, Fei,Wang, Yangyang,Lu, Faguan,Xie, Shangqing,Qi, Xinghao,Sun, Hongjian,Li, Xiaoyan,Fuhr, Olaf,Fenske, Dieter
, p. 15578 - 15586 (2018/10/04)
Polyfluorinated aryl imines 2,4,5-R1,R2,R3-C6H2-HC═N-1-C10H7 (R1 = F, R2 = F, R3 = H (1); R1 = F, R2 = H, R3 = F (2) and R1 = F, R2 = F, R3 = F (3)) and F5C6-HC═N-1-C10H7 (7) reacted with CoMe(PMe3)4 to give rise to hydrido [CNC]-pincer cobalt(iii) complexes (2,4,5-R1,R2,R3-C6H-HC═N-1-C10H6)Co(H)(PMe3)2 (R1 = F, R2 = F, R3 = H (4); R1 = F, R2 = H, R3 = F (5); R1 = F, R2 = F, R3 = F (6)) and (F4C6-HC═N-1-C10H6)Co(H)(PMe3)2 (8) via selective C-F/C-H bond activation. Penta-coordinate dicarbonyl cobalt(i) complexes (2,4,5-R1,R2,R3-C6H-HC═N-1-C10H7)Co(CO)2(PMe3) (R1 = F, R2 = H, R3 = F (9); R1 = F, R2 = F, R3 = F (10)) were obtained from reactions of hexa-coordinate cobalt(iii) complexes 5 and 6 with carbon monoxide through reductive elimination. Cobalt(iii) halides (2,4,5-R1,R2,R3-C6H-HC═N-1-C10H6)Co(i)(PMe3)2 (R1 = F, R2 = F, R3 = H (11); R1 = F, R2 = H, R3 = F (12); R1 = F, R2 = F, R3 = F (13)) and (2,4,5-R1,R2,R3-C6H-HC═N-1-C10H6)Co(Br)(PMe3)2 (R1 = F, R2 = F, R3 = H (14); R1 = F, R2 = H, R3 = F (15); R1 = F, R2 = F, R3 = F (16)) were prepared by the interaction between hydrido cobalt(iii) complexes 4-6 and MeI or EtBr. The molecular configurations of complexes 4, 8, and 11 were determined by single crystal X-ray diffraction. We then confirmed that the four hydrido cobalt(iii) complexes 4-6 and 8 could be used as catalysts for reduction of aldehydes and ketones. Complex 8 is the best catalyst among the four complexes and can selectively catalyze the carbonyl groups of α,β-unsaturated aldehydes and ketones.
Nickel-catalyzed C-F bond activation and alkylation of polyfluoroaryl imines
Yang, Xiuxiu,Sun, Hongjian,Zhang, Shumiao,Li, Xiaoyan
, p. 36 - 42 (2013/02/21)
In this paper we show the C-F bond activation and alkylation in polyfluoroaryl imines. An active trimethylphosphine supported nickel-catalyzed cross-coupling reaction of polyfluoroaryl imines with ZnMe2 under mild conditions is described. According to the in situ 19F NMR spectroscopic data, the substrates are quantitatively converted into di-methylation products, while mono-methylation can also be realized under the controlled conditions in moderate yields. Apart from ZnMe2, other organozinc regents were tried in this system. However, due to the nucleophilicity and steric hindrance, they show much lower reactivity than ZnMe2. Only in the case of benzylic zinc chloride, the dibenzylation product can be obtained quantitatively by raising temperature to 90 °C. The results reported here will benefit the development of C-F bond activation as well as the diversity of Schiff bases.
