Photochemical synthesis of tungsten pentafluoride, WF${}_5$

A new synthetic route for the synthesis of WF${}_5$ utilizing a mercury photosensitized reduction of tungsten hexafluoride with H${}_2$ is described. Crystals of WF${}_5$ were studied using single-crystal X-ray diffraction, resulting in the first-reported crystal structure of WF${}_5$. Powder X-ray diffraction studied at room-temperature showed the compound was phase-pure. The IR spectrum of WF${}_5$ was reinvestigated and interpreted with the use of solid-state quantum-chemical calculations using the DFT-PBE0 density functional method. The compound synthesized herein was free of HF and moisture but may have contained minute amounts of WOF${}_4$, that were only observed in the IR spectrum. (© 2020 The Authors. Published by Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim)