Investigation of Bis(Perfluoro‐tert‐Butoxy) Halogenates(I/III)

A systematic study of halogenate(I/III) anions with polyatomic ligands is presented. The bis(perfluoro‐tert‐butoxy) halogenates(I) [X(OC(4)F(9))(2)](−), X=Cl, Br, I, of chlorine, bromine, and iodine are prepared as their tetraethylammonium salts and characterized with IR, Raman, and NMR spectroscopic methods, as well as single‐crystal X‐ray diffraction analyses. Spectroscopical data are supported by quantum‐chemical calculations. Additionally, the bonding situation of the species in question are analyzed and discussed. Furthermore, the oxidation to the corresponding halogenate(III) derivatives was studied. For [Br(OC(4)F(9))(2)](−), oxidation with elemental fluorine gave [BrF(2)(OC(4)F(9))(2)](−). Iodide was directly oxidized by ClOC(4)F(9) to the I(III) species [I(OC(4)F(9))(4)](−), which is a surprisingly inert anion that might be used as a weakly coordinating anion (WCA) in the future. For [Cl(OC(4)F(9))(2)](−), the decomposition products of the synthetic approaches towards a chlorine(III) system were analyzed.