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<p>In single-atom catalysts, the coordination microenvironment surrounding transition-metal centers is widely recognized as a key factor shaping their electronic structures and geometries, thereby governing catalytic behaviors. However, the synergetic catalysis between metal center and ligating atoms remains underexplored in single-atom catalysis. Herein, we construct the Pd(II)-N<sub>4</sub> sites on carbon nitride to achieve photocatalytic semi-hydrogenation of alkynes. Under light irradiation, the Pd-N sites could transform to H-Pd···N-H moieties. The Pd-H center enhances alkyne insertion while the adjacent N-H group facilitates intramolecular proton transfer. This metal-ligand cooperativity of H-Pd···N-H sites, together with the steric-hindrance imposed by carbon nitride scaffold, lowers the energy barrier for <i>Z</i>-alkene formation and ensures exclusive stereoselectivity. Simultaneously, the H-Pd···N-H sites exhibit stronger adsorption toward alkynes than alkenes, effectively suppressing over-hydrogenation to alkanes. Across all evaluated substrates, <i>Z</i>-alkenes are the only isomers detected, excluding <i>E</i>-isomer and alkane. Notably, in a 5:95 mixture of diphenylacetylene and <i>Z</i>-stilbene, this method selectively converts only the alkyne to the <i>Z</i>-isomer without over-hydrogenation, highlighting its potential for product purification.</p>

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The H-Pd···N-H metal-ligand dual-atom sites synergistically catalyzed alkyne semi-hydrogenation with complete Z-selectivity

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年1月23日

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  • Haojie Ma,
  • Liwei Wang,
  • Jinming Wang,
  • Yu Yang,
  • Menglong Ma,
  • Guanglin Wang,
  • Zhizhen Ren,
  • Dandan Cui,
  • Weichang Hao,
  • Pengfei Li,
  • Peijie Ma,
  • Kun Zheng,
  • Li An,
  • Dan Qu,
  • Xiayan Wang,
  • Zaicheng Sun,
  • Yichang Liu

摘要

In single-atom catalysts, the coordination microenvironment surrounding transition-metal centers is widely recognized as a key factor shaping their electronic structures and geometries, thereby governing catalytic behaviors. However, the synergetic catalysis between metal center and ligating atoms remains underexplored in single-atom catalysis. Herein, we construct the Pd(II)-N4 sites on carbon nitride to achieve photocatalytic semi-hydrogenation of alkynes. Under light irradiation, the Pd-N sites could transform to H-Pd···N-H moieties. The Pd-H center enhances alkyne insertion while the adjacent N-H group facilitates intramolecular proton transfer. This metal-ligand cooperativity of H-Pd···N-H sites, together with the steric-hindrance imposed by carbon nitride scaffold, lowers the energy barrier for Z-alkene formation and ensures exclusive stereoselectivity. Simultaneously, the H-Pd···N-H sites exhibit stronger adsorption toward alkynes than alkenes, effectively suppressing over-hydrogenation to alkanes. Across all evaluated substrates, Z-alkenes are the only isomers detected, excluding E-isomer and alkane. Notably, in a 5:95 mixture of diphenylacetylene and Z-stilbene, this method selectively converts only the alkyne to the Z-isomer without over-hydrogenation, highlighting its potential for product purification.