Unravelling highly oxidized nickel centers in the anodic black film formed during the Simons process by X-ray absorption near edge structure spectroscopy.

The Simons process is an electrochemical fluorination method to prepare organofluorine compounds. Despite the wide application, the underlying mechanism is still unclear. We report the investigation of the black film formed on the surface of the anodes in aHF by an Ni K-edge X-ray absorption near edge structure (XANES) investigation.

Matrix Isolation Spectroscopic and Relativistic Quantum Chemical Study of Molecular Platinum Fluorides PtF (n=1-6) Reveals Magnetic Bistability of PtF.

Molecular platinum fluorides PtF , n=1-6, are prepared by two different routes, photo-initiated fluorine elimination from PtF embedded in solid noble-gas matrices, and the reaction of elemental fluorine with laser-ablated platinum atoms. IR spectra of the reaction products isolated in rare-gas matrices under cryogenic conditions provide, for the first time, experimental vibrational frequencies of molecular PtF , PtF and PtF . Photolysis of PtF enabled a highly efficient and almost quantitative formation of molecular PtF , whereas both PtF and PtF were formed simultaneously by subsequent UV irradiation of PtF .

Combining Theory and Experiment to Characterize the Voltammetric Behavior of Nickel Anodes in the Simons Process.

The Simons process, otherwise known as the electrochemical fluorination (ECF) method, is widely used in industry to electrolytically synthesize chemicals for various purposes. Even to this day, the exact mechanism of the ECF reaction remains unknown, but is believed to involve the formation of an anodic nickel fluoride film with highly oxidized nickel centers. In this study, experiments and density functional theory calculations are combined to characterize the initial anodic peak occurring at potentials typically required in an ECF cell.