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Direct synthesis of oxalic acid via oxidative CO coupling mediated by a dinuclear hydroxycarbonylcobalt(III) complex

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  • Yingzhuang Xu

    (Tianjin Key Lab for Rare Earth Materials and Applications, Nankai University)

  • Songyi Li

    (Tianjin Key Lab for Rare Earth Materials and Applications, Nankai University)

  • Huayi Fang

    (Tianjin Key Lab for Rare Earth Materials and Applications, Nankai University)

Abstract

Oxidative coupling of CO is a straightforward and economic benign synthetic route for value-added α-diketone moiety containing C2 or higher carbon compounds in both laboratory and industry, but is still undeveloped to date. In this work, a rare coplanar dinuclear hydroxycarbonylcobalt(III) complex, bearing a Schiff-base macrocyclic equatorial ligand and a μ-κ1(O):κ1(O’)-acetate bridging axial ligand, is synthesized and characterized. The Co(III)-COOH bonds in this complex can be feasibly photocleaved, leading to the formation of oxalic acid. Moreover, the light-promoted catalytic direct production of oxalic acid from CO and H2O using O2 as the oxidant with good selectivity (> 95%) and atom economy at ambient temperature and gas pressure based on this dicobalt(III) complex have been achieved, with a turnover number of 38.5. The 13C-labelling and 18O-labelling experiments confirm that CO and H2O act as the sources of the -COOH groups in the dinuclear hydroxycarbonylcobalt(III) complex and the oxalic acid product.

Suggested Citation

  • Yingzhuang Xu & Songyi Li & Huayi Fang, 2023. "Direct synthesis of oxalic acid via oxidative CO coupling mediated by a dinuclear hydroxycarbonylcobalt(III) complex," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-38442-4
    DOI: 10.1038/s41467-023-38442-4
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    1. Helen R. Sharpe & Ana M. Geer & Laurence J. Taylor & Benjamin M. Gridley & Toby J. Blundell & Alexander J. Blake & E. Stephen Davies & William Lewis & Jonathan McMaster & David Robinson & Deborah L. K, 2018. "Selective reduction and homologation of carbon monoxide by organometallic iron complexes," Nature Communications, Nature, vol. 9(1), pages 1-8, December.
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