Synergism of primary and secondary interactions in a crystalline hydrogen peroxide complex with tin.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 38982085.
- Also identified by DOI 10.1038/s41467-024-50164-9 and PMC identifier 11233698.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Despite the significance of H<sub>2</sub>O<sub>2</sub>-metal adducts in catalysis, materials science and biotechnology, the nature of the interactions between H<sub>2</sub>O<sub>2</sub> and metal cations remains elusive and debatable. This is primarily due to the extremely weak coordinating ability of H<sub>2</sub>O<sub>2</sub>, which poses challenges in characterizing and understanding the specific nature of these interactions. Herein, we present an approach to obtain H<sub>2</sub>O<sub>2</sub>-metal complexes that employs neat H<sub>2</sub>O<sub>2</sub> as both solvent and ligand. SnCl<sub>4</sub> effectively binds H<sub>2</sub>O<sub>2</sub>, forming a SnCl<sub>4</sub>(H<sub>2</sub>O<sub>2</sub>)<sub>2</sub> complex, as confirmed by <sup>119</sup>Sn and <sup>17</sup>O NMR spectroscopy. Crystalline adducts, SnCl<sub>4</sub>(H<sub>2</sub>O<sub>2</sub>)<sub>2</sub>·H<sub>2</sub>O<sub>2</sub>·18-crown-6 and 2[SnCl<sub>4</sub>(H<sub>2</sub>O<sub>2</sub>)(H<sub>2</sub>O)]·18-crown-6, are isolated and characterized by X-ray diffraction, providing the complete characterization of the hydrogen bonding of H<sub>2</sub>O<sub>2</sub> ligands including geometric parameters and energy values. DFT analysis reveals the synergy between a coordinative bond of H<sub>2</sub>O<sub>2</sub> 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<sub>2</sub>O<sub>2</sub> reactivity in biological systems.