IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v16y2025i1d10.1038_s41467-025-63914-0.html
   My bibliography  Save this article

Bimetallic [Co/K] hydrogen evolution catalyst for electrochemical terminal C-H functionalization

Author

Listed:
  • Sheng Zhang

    (Anhui University)

  • Lei Hong

    (Anhui University)

  • Jiayi Feng

    (Anhui University)

  • Mohan Wang

    (Anhui University)

  • Junyuan Hu

    (Shandong University)

  • Ying Zhang

    (Anhui University)

  • Man-Bo Li

    (Anhui University)

Abstract

Discovering novel catalysts for hydrogen evolution reaction (HER) holds the potential to revolutionize the energy chemistry and unlock new tool for synthetic processes. Inspired by hydrogenases, we pair alkali metals with cobalt-Salen catalysts which allow the integration of naked base site into bimetallic HER catalysts. The incorporation of alkali metals (Na, K, Rb, Cs) significantly enhances HER activity. Among these, the [Co/K] system exhibits the highest HER catalytic efficiency (kobs ~ 31.4 s⁻¹), which is 9 times higher than the mononuclear analogue. Remarkably, this HER catalyst is repurposed for the terminal C(sp³)-H functionalization of N-allylimines with imine/aldehyde, a previously inaccessible transformation. Mechanistic studies reveal that the naked base site enables selective C-H activation via proton relay, overriding the inherent preference for Pinacol coupling. The electrochemical protocol features good functional group tolerance, and opens up a streamlined avenue for chiral pyrrolines, key precursors of the anti-cancer medicine Larotrectinib. More importantly, the alkali metal effect is rationalized through structural analysis, density functional theory (DFT) calculations, and control experiments.

Suggested Citation

  • Sheng Zhang & Lei Hong & Jiayi Feng & Mohan Wang & Junyuan Hu & Ying Zhang & Man-Bo Li, 2025. "Bimetallic [Co/K] hydrogen evolution catalyst for electrochemical terminal C-H functionalization," Nature Communications, Nature, vol. 16(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-63914-0
    DOI: 10.1038/s41467-025-63914-0
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-025-63914-0
    File Function: Abstract
    Download Restriction: no
    File URL: https://libkey.io/10.1038/s41467-025-63914-0?utm_source=ideas
    LibKey link: if access is restricted and if your library uses this service, LibKey will redirect you to where you can use your library subscription to access this item
    ---><---

    References listed on IDEAS

    as
    1. Samer Gnaim & Adriano Bauer & Hai-Jun Zhang & Longrui Chen & Cara Gannett & Christian A. Malapit & David E. Hill & David Vogt & Tianhua Tang & Ryan A. Daley & Wei Hao & Rui Zeng & Mathilde Quertenmont, 2022. "Cobalt-electrocatalytic HAT for functionalization of unsaturated C–C bonds," Nature, Nature, vol. 605(7911), pages 687-695, May.
    2. Chen-Yan Cai & Zheng-Jian Wu & Ji-Ying Liu & Ming Chen & Jinshuai Song & Hai-Chao Xu, 2021. "Tailored cobalt-salen complexes enable electrocatalytic intramolecular allylic C–H functionalizations," Nature Communications, Nature, vol. 12(1), pages 1-9, December.
    3. Ke Liu & Mengna Lei & Xin Li & Xuemei Zhang & Ying Zhang & Weigang Fan & Man-Bo Li & Sheng Zhang, 2024. "Paired electrocatalysis unlocks cross-dehydrogenative coupling of C(sp3)-H bonds using a pentacoordinated cobalt-salen catalyst," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    4. Anzai Shi & Pengfei Xie & Yanwei Wang & Youai Qiu, 2025. "Photoelectrocatalytic Cl-mediated C(sp3)–H aminomethylation of hydrocarbons by BiVO4 photoanodes," Nature Communications, Nature, vol. 16(1), pages 1-14, December.
    Full references (including those not matched with items on IDEAS)

    Most related items

    These are the items that most often cite the same works as this one and are cited by the same works as this one.
    1. Ke Liu & Mengna Lei & Xin Li & Xuemei Zhang & Ying Zhang & Weigang Fan & Man-Bo Li & Sheng Zhang, 2024. "Paired electrocatalysis unlocks cross-dehydrogenative coupling of C(sp3)-H bonds using a pentacoordinated cobalt-salen catalyst," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    2. Tanner C. Jankins & Philip M. Blank & Andrea Brugnetti & Philip Boehm & Françoise A. Aouane & Bill Morandi, 2024. "Shuttle HAT for mild alkene transfer hydrofunctionalization," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    3. Minghui Xue & Zhiqiang Peng & Keyan Tao & Jiong Jia & Datong Song & Chen-Ho Tung & Wenguang Wang, 2024. "Catalytic hydrogenation of olefins by a multifunctional molybdenum-sulfur complex," Nature Communications, Nature, vol. 15(1), pages 1-8, December.
    4. Wen-Jie Feng & Zhe Chang & Xi Lu & Yao Fu, 2025. "Electrochemical cobalt-catalyzed semi-deuteration of alkynes to access deuterated Z-alkenes," Nature Communications, Nature, vol. 16(1), pages 1-9, December.
    5. Xiyang Cao & Yuyang Fu & Yongsheng Tao & Qingquan Lu, 2025. "Enantioselective electroreductive alkyne-aldehyde coupling," Nature Communications, Nature, vol. 16(1), pages 1-8, December.

    More about this item

    Statistics

    Access and download statistics

    Corrections

    All material on this site has been provided by the respective publishers and authors. You can help correct errors and omissions. When requesting a correction, please mention this item's handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-63914-0. See general information about how to correct material in RePEc.

    If you have authored this item and are not yet registered with RePEc, we encourage you to do it here. This allows to link your profile to this item. It also allows you to accept potential citations to this item that we are uncertain about.

    If CitEc recognized a bibliographic reference but did not link an item in RePEc to it, you can help with this form .

    If you know of missing items citing this one, you can help us creating those links by adding the relevant references in the same way as above, for each refering item. If you are a registered author of this item, you may also want to check the "citations" tab in your RePEc Author Service profile, as there may be some citations waiting for confirmation.

    For technical questions regarding this item, or to correct its authors, title, abstract, bibliographic or download information, contact: Sonal Shukla or Springer Nature Abstracting and Indexing (email available below). General contact details of provider: http://www.nature.com .

    Please note that corrections may take a couple of weeks to filter through the various RePEc services.

    IDEAS is a RePEc service. RePEc uses bibliographic data supplied by the respective publishers.