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

Hongsen Li, Boao Han, Rongyi Wang, Wentao Li, Wentao Zhang, Xuefeng Fu, Huayi Fang, Fuqiu Ma, Zikuan Wang () and Jiajing Zhang ()
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Hongsen Li: Binzhou Medical University
Boao Han: Binzhou Medical University
Rongyi Wang: Binzhou Medical University
Wentao Li: Peking University
Wentao Zhang: Peking University
Xuefeng Fu: Peking University
Huayi Fang: Nankai University
Fuqiu Ma: Yantai Research Institute of Harbin Engineering University
Zikuan Wang: Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1
Jiajing Zhang: Binzhou Medical University

Nature Communications, 2024, vol. 15, issue 1, 1-10

Abstract: 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, BrCCl3 or TEMPO under thermal or photochemical conditions afford small-molecule bimolecular reductive coupling products. To the best of our knowledge, homogeneous systems which reductively couple CO under photochemical conditions have not been reported before. Here, the use of an open-shell transition metal complex, that delivers more than one kind of small-molecule CO reductive coupling products bearing different functional groups, provides opportunities for useful CO reductive transformations.

Date: 2024
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DOI: 10.1038/s41467-024-50253-9

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