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Elucidation of hemilabile-coordination-induced tunable regioselectivity in single-site Rh-catalyzed heterogeneous hydroformylation

Author

Listed:
  • Benhan Fan

    (Dalian Institute of Chemical Physics, Chinese Academy of Sciences)

  • Miao Jiang

    (Dalian Institute of Chemical Physics, Chinese Academy of Sciences)

  • Guoqing Wang

    (Dalian Institute of Chemical Physics, Chinese Academy of Sciences)

  • Yang Zhao

    (Dalian Institute of Chemical Physics, Chinese Academy of Sciences)

  • Bingbao Mei

    (Shanghai Advanced Research Institute, Chinese Academy of Sciences)

  • Jingfeng Han

    (iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Dalian Institute of Chemical Physics, Chinese Academy of Sciences)

  • Lei Ma

    (Dalian Institute of Chemical Physics, Chinese Academy of Sciences)

  • Cunyao Li

    (Dalian Institute of Chemical Physics, Chinese Academy of Sciences)

  • Guangjin Hou

    (Dalian Institute of Chemical Physics, Chinese Academy of Sciences)

  • Tao Wu

    (Dalian University of Technology)

  • Li Yan

    (Dalian Institute of Chemical Physics, Chinese Academy of Sciences)

  • Yunjie Ding

    (Dalian Institute of Chemical Physics, Chinese Academy of Sciences
    Dalian Institute of Chemical Physics, Chinese Academy of Sciences)

Abstract

Revealing key factors that modulate the regioselectivity in heterogeneous hydroformylation requires identifying and monitoring the dynamic evolution of the truly active center under real reaction conditions. However, unambiguous in situ characterizations are still lacking. Herein, we elaborately construct a series of Rh-POPs catalysts for propylene hydroformylation which exhibited tunable regioselectivity. Multi-technique approaches reveal the unique microenvironment of the diverse HRh(CO)(PPh3-frame)2 sites with distinct P-Rh-P bite angles ranging from 90° to 120° and 158° to 168°, respectively. In situ time-resolved XAFS, FT-IR, and quasi-in situ Solid-state NMR experiments combined with DFT calculations explain the dynamic evolution of the electronic and coordinate state of the distinct active sites induced by hemilabile PPh3-frame ligands and further disclose the regulatory mechanism of regioselectivity. These state-of-the-art techniques and multiscale analysis advance the understanding of how hemilabile coordination influences regioselectivity and will provide a new thought to modulate the regioselectivity in future industrial processes.

Suggested Citation

  • Benhan Fan & Miao Jiang & Guoqing Wang & Yang Zhao & Bingbao Mei & Jingfeng Han & Lei Ma & Cunyao Li & Guangjin Hou & Tao Wu & Li Yan & Yunjie Ding, 2024. "Elucidation of hemilabile-coordination-induced tunable regioselectivity in single-site Rh-catalyzed heterogeneous hydroformylation," Nature Communications, Nature, vol. 15(1), pages 1-14, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-51281-1
    DOI: 10.1038/s41467-024-51281-1
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    1. Insoo Ro & Ji Qi & Seungyeon Lee & Mingjie Xu & Xingxu Yan & Zhenhua Xie & Gregory Zakem & Austin Morales & Jingguang G. Chen & Xiaoqing Pan & Dionisios G. Vlachos & Stavros Caratzoulas & Phillip Chri, 2022. "Bifunctional hydroformylation on heterogeneous Rh-WOx pair site catalysts," Nature, Nature, vol. 609(7926), pages 287-292, September.
    2. Zheng Chen & Zhangyun Liu & Xin Xu, 2023. "Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO2 single-atom catalyst," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    3. Peng Gao & Guanfeng Liang & Tong Ru & Xiaoyan Liu & Haifeng Qi & Aiqin Wang & Fen-Er Chen, 2021. "Phosphorus coordinated Rh single-atom sites on nanodiamond as highly regioselective catalyst for hydroformylation of olefins," Nature Communications, Nature, vol. 12(1), pages 1-10, December.
    4. Yifeng Liu & Zhiqiang Liu & Yu Hui & Liang Wang & Jian Zhang & Xianfeng Yi & Wei Chen & Chengtao Wang & Hai Wang & Yucai Qin & Lijuan Song & Anmin Zheng & Feng-Shou Xiao, 2023. "Rhodium nanoparticles supported on silanol-rich zeolites beyond the homogeneous Wilkinson’s catalyst for hydroformylation of olefins," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    5. Minjie Zhao & Chengeng Li & Daviel Gómez & Francisco Gonell & Vlad Martin Diaconescu & Laura Simonelli & Miguel Lopez Haro & Jose Juan Calvino & Debora Motta Meira & Patricia Concepción & Avelino Corm, 2023. "Low-temperature hydroformylation of ethylene by phosphorous stabilized Rh sites in a one-pot synthesized Rh-(O)-P-MFI zeolite," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
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