Lozinšek Matic, Mercier Hélène P A, Schrobilgen Gary J
Department of Chemistry, McMaster University, Hamilton, ON, L8S 4M1, Canada.
Present address: Department of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova 39, 1000, Ljubljana, Slovenia.
Angew Chem Int Ed Engl. 2021 Apr 6;60(15):8149-8156. doi: 10.1002/anie.202014682. Epub 2021 Mar 1.
The coordination chemistry of KrF has been limited in contrast with that of XeF , which exhibits a far richer coordination chemistry with main-group and transition-metal cations. In the present work, reactions of [XeF ][AsF ] with KrF in anhydrous HF solvent afforded [F Xe(FKrF)AsF ] and [F Xe(FKrF) AsF ], the first mixed krypton/xenon compounds. X-ray crystal structures and Raman spectra show the KrF ligands and [AsF ] anions are F-coordinated to the xenon atoms of the [XeF ] cations. Quantum-chemical calculations are consistent with essentially noncovalent ligand-xenon bonds that may be described in terms of σ-hole bonding. These complexes significantly extend the XeF -KrF analogy and the limited chemistry of krypton by introducing a new class of coordination compound in which KrF functions as a ligand that coordinates to xenon(VI). The HF solvates, [F Xe(FH)AsF ] and [F Xe(FH)SbF ], are also characterized in this study and they provide rare examples of HF coordinated to xenon(VI).
与XeF的配位化学相比，KrF的配位化学较为有限，XeF与主族和过渡金属阳离子表现出丰富得多的配位化学。在本工作中，[XeF][AsF]与KrF在无水HF溶剂中反应得到了[FXe(FKrF)AsF]和[FXe(FKrF)AsF]，这是首批氪/氙混合化合物。X射线晶体结构和拉曼光谱表明，KrF配体和[AsF]阴离子通过氟与[XeF]阳离子中的氙原子配位。量子化学计算结果与本质上为非共价的配体-氙键一致，这种键可用σ-空穴键来描述。这些配合物通过引入一类新型配位化合物，显著扩展了XeF - KrF的相似性以及氪有限的化学性质，在这类化合物中，KrF作为配体与六价氙配位。本研究还对HF溶剂化物[FXe(FH)AsF]和[FXe(FH)SbF]进行了表征，它们提供了HF与六价氙配位的罕见实例。
