Oxidative perfluoroorganylation methods in group 12–16 chemistry: The reactions of haloperfluoroorganics and In and InBr, a convenient new route to AgRf (Rf = CF3, C6F5) and reactions of AgRf with group 12–16 elements

Perfluoroiodo organics RfI (Rf=n-CnF2n+1 (n=1, 2, 3, 4, 6), i-C3F7, C6F5) and C6F5Br react with elemental indium in polyethers or THF to give spectroscopic evidence for compounds of the general composition InIIRfX (X=I, Br). All isolation attempts led to decomposition into InIII(Rf)2I and InII. In contrast, the reaction of In, 0.5Br2 and C6F5Br in THF selectively and quantitatively yielded In(C6F5)Br2·2THF which was structurally characterized. The reaction of In(C6F5)Br2·2THF and acetylacetone (Hacac) quantitatively gave the distorted octahedral molecule In(acac)Br2·2THF. Perfluoroorganosilver(I) compounds Ag(Rf) (Rf=CF3, C6F5) are conveniently and selectively prepared from AgF and Me3SiRf in several nitrile solvents. [PNP][AgI(CF3)2] ([PNP]=bis(triphenylphosphoranyliden)ammonium) is isolated from the reaction mixture after addition of one equivalent of [PNP]Cl. Using excess of [PNP]Cl, [PNP][AgI(CF3)Cl] is formed which is characterized by single crystal structure analysis. Besides its properties as a nucleophilic perfluoroorganylating reagent, AgRf exhibits to be an excellent oxidative perfluoroorganylation reagent in reactions with various elements of groups 12–16 to give the corresponding perfluoroorgano element compounds in moderate to excellent yields leaving elemental silver.