Exploring the Limits of Transition-Metal Fluorination at High Pressures.

Fluorination is a proven method for challenging the limits of chemistry, both structurally and electronically. Here we explore computationally how pressures below 300 GPa affect the fluorination of several transition metals. A plethora of new structural phases are predicted along with the possibility for synthesizing four unobserved compounds: TcF , CdF , OsF , and IrF . The Ir and Os octaflourides are both predicted to be stable as quasi-molecular phases with an unusual cubic ligand coordination, and both compounds formally correspond to a high oxidation state of +8. Electronic-structure analysis reveals that otherwise unoccupied 6p levels are brought down in energy by the combined effects of pressure and a strong ligand field. The valence expansion of Os and Ir enables ligand-to-metal F 2p→M 6p charge transfer that strengthens M-F bonds and decreases the overall bond polarity. The lower stability of IrF , and the instability of PtF and several other compounds below 300 GPa, is explained by the occupation of M-F antibonding orbitals in octafluorides with a metal-valence-electron count exceeding 8.