Coordination chemistry of mercury-containing anticrowns. Synthesis and structures of the complexes of cyclic trimeric perfluoro-o-phenylenemercury with ethanol, THF and bis-2,2 '-tetrahydrofuryl peroxide

摘要

Cyclic trimeric perfluoro-o-phenylenemercury (o-C6F4Hg)(3) (1) is capable of reacting with ethanol to form a 1: 1 complex, {[(o-C6F4Hg)(3)](EtOH)} (2), having a pyramidal structure. The ethanol molecule in 2 is coordinated through the oxygen atom to all Hg atoms of the macrocycle. The interaction of 1 with THF followed by drying of the product obtained in vacuum also gives the corresponding pyramidal 1: 1 complex {[(o-C6F4Hg)(3)](THF)} (3). However, when a THF solution of 1 is slowly concentrated to a small volume and the resulting crystals are not dried, three cocrystallized adducts, viz., {[(o-C6F4Hg)(3)](THF)(2)} (4), {[(o-C6F4Hg)(3)](THF)(3)} (5) and {[(o-C6F4Hg)(3)](THF)(4)} (6), containing two, three and even four THF molecules, respectively, are produced. Complex 4 has a bipyramidal structure. Complexes 5 and 6 are also characterized by the presence of a bipyramidal fragment formed by two coordinated THF species. The topological analysis of the DFT-calculated function of the electron density distribution in the crystals of 2 and 3 revealed the critical points (3, -1) on each of the three Hg center dot center dot center dot O lines, which is in accord with the X-ray diffraction data indicating on the presence of the triply coordinated Lewis base molecule in both adducts. If a THF solution of 1 is held for a month at 20 degrees C on air under stirring, a sandwich complex of 1 with previously unknown bis-2,2'-tetrahydrofuryl peroxide (THFPO) is formed. The THFPO ligand in this sandwich, {[(o-C6F4Hg)(3)](2)(THFPO)} (7), provides all its four oxygen atoms for the bonding to the molecules of 1. Two of these oxygen atoms, belonging to the tetrahydrofuryl moieties, are cooperatively bound each by three Hg atoms of the neighbouring macrocyclic unit whereas two others, belonging to the peroxide group, coordinate to a single Hg atom of the adjacent macrocycle.