Recent advances in the oxidative reactions of sulfinate salts under electrochemical conditions, and the reaction mechanism are discussed.

Three symmetric substances originating from triethyl phosphate were specifically synthesized with varying degree of fluorination at the side chain. Different concentrations of each phosphate were evaluated as co-solvent with regard to their flammability and the electrochemical cycling performance. With higher degree of fluorination and a higher amount of the phosphate in the electrolyte, the self-extinguishing time (SET), a value to determine and compare the flammability of electrolytes, could be significantly lowered to yield a non-flammable electrolyte mixture. A specifically designed SET device is introduced, which offers more accurate results due to lowered standard deviations by minimizing random and systematic errors. As the application of phosphates as co-solvents results in a trade-off in cycling performance, a thorough determination in regard to the ionic conductivity, the anodic oxidation stability and the compatibility with anode and cathode material was carried out in half- and full-cells. The manuscript strives to establish a deeper understanding of the influence that the utilization of phosphates as co-solvents entail with special focus on the fluorination degree. It could be shown that the partially fluorinated phosphate offers the best cycling results and therefore the lowest trade-off in performance, while a severe improvement in SET could be achieved compared to the reference electrolyte.

A new synthetic pathway for the N-heterocyclic carbene adduct (NHC^Me)SiCl₄ (2) (NHC^Me = 1,3-dimethylimidazolidin-2-ylidene) using silicochloroform is presented. Supported by DFT calculations, the energy for dissociation of 2 into the carbene and the SiCl₄ fragment was found to be comparable to carbene transfer reagents based on silver(I) chloride. Compound 2 was used to transfer the NHC ligand to three different phosphorus(III) chloro compounds, resulting in the neutral complexes (NHC^Me)PCl₃ (3a), (NHC^Me)PCl₂Ph (3b) and (NHC^Me)PCl₂Me (3c). The sterically non-demanding NHC ligand allowed the phosphorus(III) in complex 3a to be oxidized to phosphorus(V) without loss of the NHC ligand, and afford (NHC^Me)PF₄H (4). Furthermore, bis-carbene complexes of Ni(II) (5) and Pd(II) (6) were obtained by reacting 2 with the respective metal chlorides.