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<p>Here, we report a thioether-modified pyridine-2,6-dicarboxamide copper complex, [Cu(L)], <b>1</b> and its hydroxide-bridged dimer form, <b>2</b> exhibit different mechanisms of CO<sub>2</sub> activation. The incorporation of a thioether moiety enhances the stabilization of the Cu(I) state and improves the redox reversibility of the complex for CO<sub>2</sub> activation. While <b>1</b> monomer shows no direct reactivity toward CO<sub>2</sub> in its resting state, the µ-OH dimer <b>2</b> reacts with CO<sub>2</sub> to form a bicarbonate species, mimicking the nucleophilic CO<sub>2</sub> hydration observed in Zn-containing carbonic anhydrases. In comparison, upon reduction, <b>1</b> forms a CO<sub>2</sub>-bound intermediate, revealing a redox-triggered pathway distinct from that of <b>2</b>. Under electrochemical conditions, both complexes exhibit irreversible Cu(II/I) reduction in the presence of CO<sub>2</sub>, wherein an initial electron-transfer (E) step is followed by a chemical (C) transformation involving transient Cu-CO<sub>2</sub> (EC-type) adduct formation. Overall, these findings demonstrate that the incorporation of soft sulfur donors equips copper complexes to mediate CO<sub>2</sub> reactivity, providing a new direction toward the design of copper-based catalysts for CO<sub>2</sub> conversion. </p>

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The development of bioinspired copper complexes for CO2 activation and hydration

  • 期刊论文

  • 发表日期：

    2026年6月22日

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  • Ramamoorthy Ramasubramanian,
  • Jyun-Chi Lee,
  • Rui-Ze Xu,
  • Xylon Weng,
  • Tiow-Gan Ong,
  • Sodio C. N. Hsu,
  • Glenn P. A. Yap,
  • Vincent C.-C. Wang

摘要

Here, we report a thioether-modified pyridine-2,6-dicarboxamide copper complex, [Cu(L)], 1 and its hydroxide-bridged dimer form, 2 exhibit different mechanisms of CO2 activation. The incorporation of a thioether moiety enhances the stabilization of the Cu(I) state and improves the redox reversibility of the complex for CO2 activation. While 1 monomer shows no direct reactivity toward CO2 in its resting state, the µ-OH dimer 2 reacts with CO2 to form a bicarbonate species, mimicking the nucleophilic CO2 hydration observed in Zn-containing carbonic anhydrases. In comparison, upon reduction, 1 forms a CO2-bound intermediate, revealing a redox-triggered pathway distinct from that of 2. Under electrochemical conditions, both complexes exhibit irreversible Cu(II/I) reduction in the presence of CO2, wherein an initial electron-transfer (E) step is followed by a chemical (C) transformation involving transient Cu-CO2 (EC-type) adduct formation. Overall, these findings demonstrate that the incorporation of soft sulfur donors equips copper complexes to mediate CO2 reactivity, providing a new direction toward the design of copper-based catalysts for CO2 conversion.