A Homoleptic KrF2 Complex, [Hg(KrF2)8][AsF6]2⋅2 HF

• Published in: Angewandte Chemie 2018-10, Vol.130 (40), p.13351-13355
• Main Authors: DeBackere, John R., Schrobilgen, Gary J.
• Format: Article
• Language: English
• Subjects: Einkristall-Röntgenbeugung; Homoleptische Komplexe; Krypton-Chemie; Quecksilber-Koordinationskomplexe; Raman-Spektroskopie
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201807755

The reaction of Hg(AsF6)2 with a large molar excess of KrF2 in anhydrous HF has afforded the first homoleptic KrF2 coordination complex of a metal cation, [Hg(KrF2)8][AsF6]2⋅2 HF. The [Hg(KrF2)8]2+ dication is well‐isolated in the low‐temperature crystal structure of its HF‐solvated [AsF6]− salt, and consists of eight KrF2 molecules that are terminally coordinated to Hg2+ by means of Hg−F(KrF) bonds to form a slightly distorted, square‐antiprismatic coordination sphere around mercury. The Raman spectrum of [Hg(KrF2)8]2+ was assigned with the aid of calculated gas‐phase vibrational frequencies. Computational studies indicate that both electrostatic and orbital interactions are important for metal–ligand bonding and provide insight into the geometry of the [Hg(KrF2)8]2+ cation and the nature of noble‐gas difluoride ligand bonding. Quecksilber schnappt sich KrF2, um die Grenzen der Edelgaschemie durch die Bildung des ersten homoleptischen Koordinationskomplexes von KrF2 zu erweitern. Das Salz [Hg(KrF2)8][AsF6]2⋅2 HF wurde kristallographisch und Raman‐spektroskopisch untersucht und besteht aus quadratisch‐antiprismatischen [Hg(KrF2)8]2+‐Kationen, in denen acht KrF2‐Moleküle über Fluor an Quecksilber binden.