Complexation of [9]Thiacrown-3 and 1,3,5-trithiane with cyclic trimeric perfluoro-o-phenylenemercury. Synthesis and structures of the first complexes of crown compounds with an anticrown

摘要

The interaction of the three-mercury anticrown (o-C6F4Hg)(3) (1) with a 5-fold excess of [9]thiacrown-3 gives a 1: 1 complex, {[(0-C6F4Hg)(3)](C2H4S)(3)} (2), representing a polydecker bent sandwich in the crystal. Every thiacrown ligand in this sandwich is bound to the nearest anticrown units by two sulfur atoms, each of which interacts with a single Hg center of the neighboring molecule of 1. When the reaction of 1 with [9]thiacrown-3 is conducted at a 2-fold excess of 1, a complex, {[(o-C6F4Hg)(3)](2)(C2H4S)(3)} (3), containing two molecules,of the mercury anticrown per one thiacrown molecule is produced, and this adduct has a double-decker sandwich structure. Here, all three sulfur atoms of the thiacrown are involved in the bonding to the molecules of the anticrown, two of them being cooperatively coordinated each by all three Lewis acidic Hg sites of the adjacent anticrown molecule, whereas the third sulfur atom interacts again with a single Hg center. From the reaction of 1 with 1,3,5-trithiane, a 1:1 complex, {[(o-C6F4Hg)(3)](CH2S)(3)} (4), has been isolated. This complex, in contrast to 2, has a discrete, cage structure. The synthesized adducts are the first complexes of crown compounds with an anticrown.