| Autor: |
Huang XK; MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275 Guangdong, China., Li LP; MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275 Guangdong, China., Zhou HY; Instrumental Analysis and Research Center, Sun Yat-sen University, Guangzhou 510275 Guangdong, China., Xiong MF; MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275 Guangdong, China., Fan JY; MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275 Guangdong, China., Ye BH; MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275 Guangdong, China. |
| Abstrakt: |
The selective photoreactions under mild conditions play an important role in synthetic chemistry. Herein, efficient and mild protocols for switching the photoreactions of Ir(III)-diamine complexes between the interligand C-N coupling and dehydrogenation are developed in the presence of O 2 in EtOH solution. The photoreactions of achiral diamine complexes rac -[Ir(L) 2 (dm)](PF 6 ) (L is 2-phenylquinoline or 2-(2,4-difluorophenyl)quinoline, dm is 1,2-ethylenediamine, 1,2-diaminopropane, 2-methyl-1,2-diamino-propane, or N , N' -dimethyl-1,2-ethylenediamine) are competitive in the oxidative C-N coupling and dehydrogenation at room temperature, which can be switched into the interligand C-N coupling reaction at 60 °C, affording hexadentate complexes in good to excellent yields, or the dehydrogenative reaction in the presence of a catalytic amount of TEMPO as an additive, affording imine complexes. Mechanism studies reveal that 1 O 2 is the major reactive oxygen species, and metal aminyl is the key intermediate in the formation of the oxidative C-N coupling and imine products in the photoreaction processes. These will provide a new and practical protocol for the synthesis of multidentate and imine ligands in situ via the postcoordinated strategy under mild conditions. |
