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Preparation of hydrido [CNC]-pincer cobalt complexes via selective C-H/C-F bond activation and their catalytic performances

Abstract

Abstract 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 in diethyl ether 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 the 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)) could be 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. It has been 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 ,-unsaturated aldehydes and ketones.

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Publication details

The article was received on 15 Jun 2018, accepted on 06 Aug 2018 and first published on 07 Aug 2018


Article type: Paper
DOI: 10.1039/C8NJ02979B
Citation: New J. Chem., 2018, Accepted Manuscript
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    Preparation of hydrido [CNC]-pincer cobalt complexes via selective C-H/C-F bond activation and their catalytic performances

    F. Yang, Y. Wang, F. Lu, S. xie, X. Qi, H. Sun, X. Li, O. fuhr and D. Fenske, New J. Chem., 2018, Accepted Manuscript , DOI: 10.1039/C8NJ02979B

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