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, М. Н. Бреховских, Anna A. Kirsanova, Maria V. Babak, Ovadia Lev, Petr V. Prikhodchenko
Abstract
Abstract Despite the significance of H 2 O 2 -metal adducts in catalysis, materials science and biotechnology, the nature of the interactions between H 2 O 2 and metal cations remains elusive and debatable. This is primarily due to the extremely weak coordinating ability of H 2 O 2 , which poses challenges in characterizing and understanding the specific nature of these interactions. Herein, we present an approach to obtain H 2 O 2 –metal complexes that employs neat H 2 O 2 as both solvent and ligand. SnCl 4 effectively binds H 2 O 2 , forming a SnCl 4 (H 2 O 2 ) 2 complex, as confirmed by 119 Sn and 17 O NMR spectroscopy. Crystalline adducts, SnCl 4 (H 2 O 2 ) 2 ·H 2 O 2 ·18-crown-6 and 2[SnCl 4 (H 2 O 2 )(H 2 O)]·18-crown-6, are isolated and characterized by X-ray diffraction, providing the complete characterization of the hydrogen bonding of H 2 O 2 ligands including geometric parameters and energy values. DFT analysis reveals the synergy between a coordinative bond of H 2 O 2 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 H 2 O 2 reactivity in biological systems.