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 (R-f = 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 (InRfX)-R-II (X = I, Br). All isolation attempts led to decomposition into In-III(R-f)(2)I and (InI)-I-I. In contrast, the reaction of In, 0.5Br(2) and C6F5Br in THF selectively and quantitatively yielded In(C6F5)Br-2. 2THF which was structurally characterized. The reaction of In(C6F5)Br-2. 2THF and acetylacetone (Hacac) quantitatively gave the distorted octahedral molecule In(acac)Br-2.2THF. Perfluoroorganosilver(I) compounds Ag(R-f) (R-f = CF3, C6F5) are conveniently and selectively prepared from A-F and Me3SiRf in several nitrile solvents. [PNP][Ag-1(CF3)(2)] [PNP] = bis(triphenylphosphoranyliden)ammo-PNP][Ag-1(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. (C) 2001 Elsevier Science B.V. All rights reserved.