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Outpacing conventional nicotinamide hydrogenation catalysis by a strongly communicating heterodinuclear photocatalyst

Author

Listed:
  • Linda Zedler

    (Friedrich Schiller University Jena
    Leibniz Institute of Photonic Technology Jena, Department Functional Interfaces)

  • Pascal Wintergerst

    (Ulm University)

  • Alexander K. Mengele

    (Ulm University)

  • Carolin Müller

    (Friedrich Schiller University Jena
    Leibniz Institute of Photonic Technology Jena, Department Functional Interfaces)

  • Chunyu Li

    (Friedrich Schiller University Jena
    Leibniz Institute of Photonic Technology Jena, Department Functional Interfaces)

  • Benjamin Dietzek-Ivanšić

    (Friedrich Schiller University Jena
    Leibniz Institute of Photonic Technology Jena, Department Functional Interfaces
    Center for Energy and Environmental Chemistry Jena (CEEC Jena))

  • Sven Rau

    (Ulm University)

Abstract

Unequivocal assignment of rate-limiting steps in supramolecular photocatalysts is of utmost importance to rationally optimize photocatalytic activity. By spectroscopic and catalytic analysis of a series of three structurally similar [(tbbpy)2Ru-BL-Rh(Cp*)Cl]3+ photocatalysts just differing in the central part (alkynyl, triazole or phenazine) of the bridging ligand (BL) we are able to derive design strategies for improved photocatalytic activity of this class of compounds (tbbpy = 4,4´-tert-butyl-2,2´-bipyridine, Cp* = pentamethylcyclopentadienyl). Most importantly, not the rate of the transfer of the first electron towards the RhIII center but rather the rate at which a two-fold reduced RhI species is generated can directly be correlated with the observed photocatalytic formation of NADH from NAD+. Interestingly, the complex which exhibits the fastest intramolecular electron transfer kinetics for the first electron is not the one that allows the fastest photocatalysis. With the photocatalytically most efficient alkynyl linked system, it is even possible to overcome the rate of thermal NADH formation by avoiding the rate-determining β-hydride elimination step. Moreover, for this photocatalyst loss of the alkynyl functionality under photocatalytic conditions is identified as an important deactivation pathway.

Suggested Citation

  • Linda Zedler & Pascal Wintergerst & Alexander K. Mengele & Carolin Müller & Chunyu Li & Benjamin Dietzek-Ivanšić & Sven Rau, 2022. "Outpacing conventional nicotinamide hydrogenation catalysis by a strongly communicating heterodinuclear photocatalyst," Nature Communications, Nature, vol. 13(1), pages 1-13, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-30147-4
    DOI: 10.1038/s41467-022-30147-4
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    Cited by:

    1. Qitao Chen & Baodong Mao & Yanhong Liu & Yunjie Zhou & Hui Huang & Song Wang & Longhua Li & Wei-Cheng Yan & Weidong Shi & Zhenhui Kang, 2024. "Designing 2D carbon dot nanoreactors for alcohol oxidation coupled with hydrogen evolution," Nature Communications, Nature, vol. 15(1), pages 1-14, December.

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