Direct synthesis of oxalic acid via oxidative CO coupling mediated by a dinuclear hydroxycarbonylcobalt(III) complex.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 37173323.
- Also identified by DOI 10.1038/s41467-023-38442-4 and PMC identifier 10182058.
- Licence recorded as CC BY.
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Abstract
Oxidative coupling of CO is a straightforward and economic benign synthetic route for value-added α-diketone moiety containing C<sub>2</sub> 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-κ<sup>1</sup>(O):κ<sup>1</sup>(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 H<sub>2</sub>O using O<sub>2</sub> 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 <sup>13</sup>C-labelling and <sup>18</sup>O-labelling experiments confirm that CO and H<sub>2</sub>O act as the sources of the -COOH groups in the dinuclear hydroxycarbonylcobalt(III) complex and the oxalic acid product.