Motaln Klemen, Gurung Kshitij, Dragomir Mirela, Kurzydłowski Dominik, Palatinus Lukáš, Lozinšek Matic
Jožef Stefan Institute, Jamova cesta 39, 1000 Ljubljana, Slovenia.
Jožef Stefan International Postgraduate School, Jamova cesta 39, 1000 Ljubljana, Slovenia.
Inorg Chem. 2025 Jul 28;64(29):14968-14976. doi: 10.1021/acs.inorgchem.5c01740. Epub 2025 Jul 14.
Although the demonstration of noble-gas reactivity represents one of the most significant breakthroughs of 20th-century inorganic chemistry, the first noble-gas compound, XePtF (XeF·PtF), lacks comprehensive structural characterization, and its structure remains to be elucidated. In this study, the XeF-PtF and XeF-PdF systems were reexplored, resulting in the crystal structure determination of XeF·2PtF and XeF·2PdF by 3D electron diffraction, marking the first successful structural characterization of compounds from these systems. Both compounds are isostructural with the previously characterized XeF·2MnF, featuring corrugated zigzag double-chain motifs formed by interconnected octahedral fluoridometallate(IV) units. Periodic density functional theory calculations were employed to evaluate the structural models of XeF·PtF, which were derived from experimentally determined crystal structures of XeF-MF (M = Cr, Mn) analogues. The results reveal a preference for -bridging between adjacent platinum(IV) centers and show that a tetrameric ring structure and -chain polymorph, modeled after the crystal structure of XeF·MnF and XeF-deficient 3XeF·2MnF, respectively, emerge as energetically favored. The results of this study thus provide a direct structural link between platinum, palladium, and manganese analogues in the XeF-MF systems and highlight the tetrameric ring structure and -chain as likely structural models of XeF·PtF.
尽管稀有气体反应性的证明是20世纪无机化学最重要的突破之一，但首个稀有气体化合物XePtF₆（XeF·PtF₅）缺乏全面的结构表征，其结构仍有待阐明。在本研究中，对XeF₆-PtF₅和XeF₆-PdF₅体系进行了重新探索，通过三维电子衍射确定了XeF₆·2PtF₅和XeF₆·2PdF₅的晶体结构，这标志着这些体系中化合物首次成功进行结构表征。这两种化合物与先前表征的XeF₆·2MnF₃同构，具有由相互连接的八面体氟金属酸盐（IV）单元形成的波纹状锯齿双链结构。采用周期性密度泛函理论计算来评估XeF₆·PtF₅的结构模型，这些模型源自XeF₆-MF₅（M = Cr、Mn）类似物的实验测定晶体结构。结果表明相邻铂（IV）中心之间倾向于桥连，并且表明分别以XeF₆·MnF₃和缺XeF₆的3XeF₆·2MnF₃晶体结构为模型的四聚环结构和链状多晶型体在能量上更有利。因此，本研究结果在XeF₆-MF₅体系中的铂、钯和锰类似物之间提供了直接的结构联系，并突出了四聚环结构和链状结构作为XeF₆·PtF₅可能的结构模型。
