Anionic Complexes of the Perfluorinated Three‐Mercury Anticrown (o,o’‐C6F4C6F4Hg)3. Dependence of the Anion Coordination Type on Counter‐Cation in Case of Chloride and Bromide Anions

Abstract

AbstractThe interaction of the macrocycle (o,o′‐C6F4C6F4Hg)3 (1) containing three mercury centres with arylphosphonium salts ([Ph4P]Cl or [Ph4P]Br) yields halide complexes, [Ph4P]{[(o,o′‐C6F4C6F4Hg)3](η1:η1‐X)} (X=Cl, Br) having infinite polymer chain structure in the crystal. In both adducts, the halide anion is situated outside of the cavity of the three‐mercury anticrown 1 and bridged by two mercury centres of neighbouring anticrown moieties. At the same time, when mercuracycle 1 interacts with tetraalkylammonium salts ([nBu4N]Cl or [nBu4N]Br), then the discrete 1 : 1 complexes [nBu4N]{[(o,o′‐C6F4C6F4Hg)3](η3‐X)} (X=Cl, Br) of completely different structure are formed. In these halide complexes the anion is located inside the cavity of macrocycle 1 and coordinates the three mercury atoms symmetrically. The synthesized halide complexes [nBu4N]{[(o,o′‐C6F4C6F4Hg)3](η3‐X)} (X=Cl, Br) are the first example of complexes of the macrocycle 1 where it behaves as anticrown.