Medvedev Alexander G, Egorov Pavel A, Mikhaylov Alexey A, Belyaev Evgeny S, Kirakosyan Gayane A, Gorbunova Yulia G, Filippov Oleg A, Belkova Natalia V, Shubina Elena S, Brekhovskikh Maria N, Kirsanova Anna A, Babak Maria V, Lev Ovadia, Prikhodchenko Petr V
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russian Federation.
Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, Moscow, Russian Federation.
Nat Commun. 2024 Jul 9;15(1):5758. doi: 10.1038/s41467-024-50164-9.
Despite the significance of HO-metal adducts in catalysis, materials science and biotechnology, the nature of the interactions between HO and metal cations remains elusive and debatable. This is primarily due to the extremely weak coordinating ability of HO, which poses challenges in characterizing and understanding the specific nature of these interactions. Herein, we present an approach to obtain HO-metal complexes that employs neat HO as both solvent and ligand. SnCl effectively binds HO, forming a SnCl(HO) complex, as confirmed by Sn and O NMR spectroscopy. Crystalline adducts, SnCl(HO)·HO·18-crown-6 and 2[SnCl(HO)(HO)]·18-crown-6, are isolated and characterized by X-ray diffraction, providing the complete characterization of the hydrogen bonding of HO ligands including geometric parameters and energy values. DFT analysis reveals the synergy between a coordinative bond of HO 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 HO reactivity in biological systems.
尽管羟基-金属加合物在催化、材料科学和生物技术中具有重要意义，但羟基与金属阳离子之间相互作用的本质仍然难以捉摸且存在争议。这主要是由于羟基的配位能力极其微弱，这给表征和理解这些相互作用的具体性质带来了挑战。在此，我们提出一种获得羟基-金属配合物的方法，该方法使用纯羟基作为溶剂和配体。通过锡和氧的核磁共振光谱证实，氯化锡有效地结合羟基，形成氯化锡（羟基）配合物。分离出结晶加合物氯化锡（羟基）·羟基·18-冠-6和2[氯化锡（羟基）（羟基）]·18-冠-6，并通过X射线衍射对其进行表征，从而全面表征了羟基配体的氢键，包括几何参数和能量值。密度泛函理论分析揭示了羟基与金属阳离子的配位键及其与第二配位层的氢键之间的协同作用。这种一级和二级相互作用的协同作用可能是理解羟基在生物系统中反应活性的关键。
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