Coordination Chemistry of Anticrowns. Synthesis and Structures of Double-Decker Sandwich Complexes of the Three-Mercury Anticrown (o-C6F4Hg)3 with Halide Anions Containing and Not Containing Coordinated Dibromomethane Molecules

Abstract

The interaction of the three-mercury anticrown (o-C6F4Hg)3 (1) with [PPh4][BF4] in methanol at room temperature leads to fluoride anion transfer from BF4– to 1 with the formation of a fluoride complex, [PPh4]{[(o-C6F4Hg)3]2F}, having a double-decker sandwich structure. The fluoride ion in this unique adduct is disposed between the mutually parallel planes of the central nine-membered rings of the anticrown units and cooperatively coordinated by all six Hg sites. The iodide anion also forms a double-decker sandwich in the interaction with 1, but this sandwich, [PPh4]{[(o-C6F4Hg)3]2I}, has a wedge-shaped geometry. The reaction of 1 with [nBu4N]Cl in dibromomethane at −15 °C affords a complex, [nBu4N]{[(o-C6F4Hg)3]2Cl(CH2Br2)2}, containing one chloride anion and two coordinated CH2Br2 species per two molecules of 1. A similar bromide complex of 1, containing two coordinated CH2Br2 moieties, has also been synthesized and structurally characterized. Both compounds represent wedge-shaped double-decker sandwiche...