Coordination chemistry of mercury-containing anticrowns. Self-assembly of unusual supramolecular aggregates in the interaction of the three-mercury anticrown (o-C6F4Hg)3 with crown ethers in the presence of neutral monodentate oxygenous Lewis bases

Coordination Chemistry of Anticrowns. Interaction of the Perfluorinated Three-Mercury Anticrown (o-C6F4Hg)3 with Azacrowns

“…Indeed, we have previously shown that macrocycle 1 is able to form complexes with crown ethers and thiacrowns at room temperature. 11,16,21 Interestingly, the reactions of 1 with crown ethers proved to be very sensitive to the presence of traces of moisture in the system, as a result of which the complexes isolated here contained, as a rule, those or other amounts of water besides the crown ether molecules in spite of carrying out the reaction under strictly anhydrous conditions. 16,21 An especially interesting complex was obtained in the interaction of 1 with [18]crown-6 in dry CH 2 Cl 2 under Ar.…”

“…Another unexpected result is a selfassembly of supramolecular aggregates {[(o-C 6 F 4 Hg) 3 ] 2 ([18]crown-6)(H 2 O) 2 L 2 } (where L is MeOH or Me 2 CO) in the interaction of 1 with [18]crown-6 in methanol or acetone as solvents. 21 Finally, it has been found that the reactions of 1 with the simplest representatives of crown ethers and thiacrowns, viz., 1,3,5-trioxane (CH 2 O) 3 and 1,3,5-trithiane (CH 2 S) 3 , give 1:1 adducts with unprecedented cage structures. 11,16 In the present article, the data obtained on studying the interaction of 1 with azacrowns are reported.…”

“…11,16,21 Interestingly, the reactions of 1 with crown ethers proved to be very sensitive to the presence of traces of moisture in the system, as a result of which the complexes isolated here contained, as a rule, those or other amounts of water besides the crown ether molecules in spite of carrying out the reaction under strictly anhydrous conditions. 16,21 An especially interesting complex was obtained in the interaction of 1 with [18]crown-6 in dry CH 2 Cl 2 under Ar. 16 In this double-decker sandwich complex, {[(o-C 6 F 4 Hg) 3 ] 2 ([18]crown-6)(H 2 O) 2 }, containing two triply coordinated water species, all six Hg atoms of the anticrown molecules and all six oxygen atoms of [18]crown-6 are involved in the bonding.…”

“…The first successful attempts to realize such an approach have been undertaken in the late 1980s to the early 1990s (see reviews − ). The results of these studies have shown that the greatest complexing ability among tested macrocyclic multidentate Lewis acids is exhibited by polymercuramacrocycles with electron-withdrawing perfluorohydrocarbon and o -carborane backbones (e.g., see the reviews cited in refs − and papers cited in refs − ). The most studied among them is perfluorinated three-mercury anticrown ( o -C 6 F 4 Hg) 3 ( 1 ) (Chart ), which has a planar structure , and is capable of effectively binding various anions and neutral Lewis bases to afford complexes wherein the Lewis basic species is simultaneously coordinated with all Hg centers of the macrocycle.…”

“…A similar type of cooperative bonding is characteristic for complexes of metal cations with crown compounds, so one might expect that these charge-reversed analogues containing several Lewis acidic and, correspondingly, several Lewis basic centers in the chain, will readily react with each other. Indeed, we have previously shown that macrocycle 1 is able to form complexes with crown ethers and thiacrowns at room temperature. ,, Interestingly, the reactions of 1 with crown ethers proved to be very sensitive to the presence of traces of moisture in the system, as a result of which the complexes isolated here contained, as a rule, those or other amounts of water besides the crown ether molecules in spite of carrying out the reaction under strictly anhydrous conditions. , An especially interesting complex was obtained in the interaction of 1 with [18]­crown-6 in dry CH 2 Cl 2 under Ar . In this double-decker sandwich complex, {[( o -C 6 F 4 Hg) 3 ] 2 ([18]­crown-6)­(H 2 O) 2 }, containing two triply coordinated water species, all six Hg atoms of the anticrown molecules and all six oxygen atoms of [18]­crown-6 are involved in the bonding.…”