Synergism of primary and secondary interactions in a crystalline hydrogen peroxide complex with tin

Alexander G. Medvedev, Pavel A. Egorov, Alexey A. Mikhaylov, Evgeny S. Belyaev, Gayane A. Kirakosyan, Yulia G. Gorbunova, Oleg A. Filippov, Natalia V. Belkova, Elena S. Shubina, Maria N. Brekhovskikh, Anna A. Kirsanova, Maria V. Babak (), Ovadia Lev () and Petr V. Prikhodchenko ()
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Alexander G. Medvedev: Russian Academy of Sciences
Pavel A. Egorov: Russian Academy of Sciences
Alexey A. Mikhaylov: Russian Academy of Sciences
Evgeny S. Belyaev: Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences
Gayane A. Kirakosyan: Russian Academy of Sciences
Yulia G. Gorbunova: Russian Academy of Sciences
Oleg A. Filippov: Russian Academy of Sciences
Natalia V. Belkova: Russian Academy of Sciences
Elena S. Shubina: Russian Academy of Sciences
Maria N. Brekhovskikh: Russian Academy of Sciences
Anna A. Kirsanova: City University of Hong Kong
Maria V. Babak: City University of Hong Kong
Ovadia Lev: Hebrew University of Jerusalem
Petr V. Prikhodchenko: Russian Academy of Sciences

Nature Communications, 2024, vol. 15, issue 1, 1-8

Abstract: Abstract Despite the significance of H2O2-metal adducts in catalysis, materials science and biotechnology, the nature of the interactions between H2O2 and metal cations remains elusive and debatable. This is primarily due to the extremely weak coordinating ability of H2O2, which poses challenges in characterizing and understanding the specific nature of these interactions. Herein, we present an approach to obtain H2O2–metal complexes that employs neat H2O2 as both solvent and ligand. SnCl4 effectively binds H2O2, forming a SnCl4(H2O2)2 complex, as confirmed by 119Sn and 17O NMR spectroscopy. Crystalline adducts, SnCl4(H2O2)2·H2O2·18-crown-6 and 2[SnCl4(H2O2)(H2O)]·18-crown-6, are isolated and characterized by X-ray diffraction, providing the complete characterization of the hydrogen bonding of H2O2 ligands including geometric parameters and energy values. DFT analysis reveals the synergy between a coordinative bond of H2O2 with metal cation and its hydrogen bonding with a second coordination sphere. This synergism of primary and secondary interactions might be a key to understanding H2O2 reactivity in biological systems.

Date: 2024
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DOI: 10.1038/s41467-024-50164-9

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