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Mono- and dinuclear zinc complexes bearing identical bis(thiosemicarbazone) ligand that exhibit alkaline phosphatase-like catalytic reactivity

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Abstract

Mono- and dinuclear zinc(II) complexes bearing bis(thiosemicarbazone) (bTSC) ligand were employed in the cleavage of phosphoester bonds. Comparative kinetic studies combined with theory suggested that the P–O bond cleavage is much accelerated by dinuclear zinc(II) complex in the presence of base. Based on the DFT-optimized structures of the proposed intermediates, it is plausible that (1) the removal of sulfur atoms of bTSC ligand from the zinc center provides two vacant sites for the binding of water (or hydroxide ion) and phosphoester and (2) the H-bonding between water (or hydroxide ion) and phosphoester, through several water molecules, may also assist the P–O bond cleavage and facilitate the nucleophilic attack. The kinetic and catalytic studies on the hydrolysis of phosphoester by dinuclear zinc complex showed a much-enhanced reactivity under basic reaction conditions, reaching over 95% conversion yield within 4 h. The currently presented compounds are arguably one of the faster synthetic Zn-based model performing phosphatase-like activity presented so far.

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Acknowledgements

This work was supported by NRF of Korea through MSIP (NRF-2020R1C1C1008886 to S.H and 2021R1A2C1012851 to K.-B.C.).

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Author notes

  1. Hugo Vazquez-Lima

    Present address: Department of Inorganic Chemistry, Meritorious Autonomous University of Puebla, 72000, Puebla, Mexico

  2. Hyeri Jeon and Hugo Vazquez-Lima have contributed equally to this manuscript.

Authors and Affiliations

  1. Department of Chemistry, Sookmyung Women’s University, Seoul, 04310, Republic of Korea

    Hyeri Jeon, Haewon Jeong & Seungwoo Hong

  2. Department of Chemistry, Jeonbuk National University, Jeonju, 54896, Republic of Korea

    Hugo Vazquez-Lima & Kyung-Bin Cho

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  1. Hyeri Jeon
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Jeon, H., Vazquez-Lima, H., Jeong, H. et al. Mono- and dinuclear zinc complexes bearing identical bis(thiosemicarbazone) ligand that exhibit alkaline phosphatase-like catalytic reactivity. J Biol Inorg Chem 27, 37–47 (2022). https://doi.org/10.1007/s00775-021-01909-0

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