| Autor: |
Xiong MF; MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou, Guangdong 510275, China., Liu GF; MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou, Guangdong 510275, China., Ye BH; MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou, Guangdong 510275, China. |
| Jazyk: |
angličtina |
| Zdroj: |
Inorganic chemistry [Inorg Chem] 2023 Jul 24; Vol. 62 (29), pp. 11654-11664. Date of Electronic Publication: 2023 Jul 13. |
| DOI: |
10.1021/acs.inorgchem.3c01441 |
| Abstrakt: |
The construction of C-S bonds is of great importance in the field of synthetic and medicinal chemistry. Herein, solvent-induced umpolung reactions from dioxygenation to interligand C-S cross-coupling in bis(cyclometalated) Ir(III) thiolate complexes are reported in good to excellent yields at room temperature. Specifically, the reaction of rac -[Ir(pq) 2 (aet)] (where pq is 2-phenylquinoline and aet is 2-aminoethanethiolate) can be selectively switched to dioxygenation in acetonitrile solution in the presence of O 2 , resulting in the formation of a sulfinato complex rac -[Ir(pq) 2 (aes)] (where aes is 2-aminoethanesulfinato). Alternatively, the reaction in trifluoroethanol solution leads to interligand C-S cross-coupling, affording a rac -[Ir(pq)(pqaet)](PF 6 ) [where pqaet is 2-((2-phenylquinolin-8-yl)thio)ethan-1-amine] complex, which generates a new tetradentate ligand in situ. Mechanistically, the formation of electrophilic metal thiyl radicals is proposed as a key intermediate in the interligand C-S coupling reaction. Furthermore, the sequential oxidation of a thioether complex into a sulfoxide complex is also observed at room temperature using H 2 O 2 as an oxidant. Additionally, a new approach for the synthesis of a hexadentate ligand is developed through sequential C-S and C-N interligand coupling of metal thiolate complexes in situ under visible light irradiation in the presence of O 2 . |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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