Photochemical conversion of CO to C1 and C2 products mediated by porphyrin rhodium(II) metallo-radical complexes.

ABSTRACT: Unimolecular reduction and bimolecular reductive coupling of carbon monoxide (CO) represent important ways to synthesize organic feedstocks. Reductive activation of CO through open-shell pathways, though rare, can help overcome the barriers of many traditional organometallic elementary reactions that are hard to achieve. Herein we successfully achieve the unimolecular reduction of CO to (TPP)RhCH2OSiR1R2R3 (TPP = 5,10,15,20-tetraphenylporphyrin), and the release of products CH3OSiR1R2R3, TEMPO-CH2OSiR1R2R3 and BrCH2OSiR1R2R3 in near-quantitative yield under visible light (420-780 nm), which involves radical formation from Rh-C bond homolysis. Bimolecular CO reductive coupling products, (TPP)RhCOCH2OSiR1R2R3, are then obtained via a radical mechanism. Subsequent treatment with n-propylamine

SUBMITTER: Li H 

PROVIDER: S-EPMC11374781 | biostudies-literature | 2024 Sep

REPOSITORIES: biostudies-literature