Treatment of 3,5-diisopropyltriazole, 3,5-diphenyltriazole, 3,5-di-3-pyridyltriazole, phenyltetrazole, pyrrolidinyltetrazole, or tert-butyltetrazole with equimolar quantities of potassium hydride and 18-crown-6 in tetrahydrofuran at ambient temperature led to slow hydrogen evolution and formation of (3,5-diisopropyl-1,2,4-triazolato)(18-crown-6)potassium (88%), (3,5-diphenyl-1,2,4-triazolato)(t...

The transport of Pb2+ through a sensory gel, a polymerized crystalline colloidal array hydrogel with immobilized benzo-18-crown-6, is important for understanding and optimizing the sensor. Square wave voltammetry at a Hg/Au electrode reveals many parameters. The partition coefficient for Pb2+ into a control gel (no crown ether), K(p), is 1.00 +/- 0.018 (errors reported are SEM). The porosity, e...

We describe the synthesis of a cyapho(dicyano)methanide salt, [K(18-crown-6)][C(CN)2(CP)], from reaction [Na(18-crown-6)][PH2] (18-crown-6=1,4,7,10,13,16-hexaoxacyclooctadecane) with 1,1-diethoxy-2,2-dicyanoethylene (EtO)2C=C(CN)2. The proceeds through Michael addition-elimination pathway to afford [Na(18-crown-6)][HP{C(OEt)=C(CN)2}]. Addition strong, non-nucleophilic base (KHMDS) this intermed...

The discovery of the crown ethers stemmed from efforts to control the catalytic activity of vanadium and copper by complexation with multidentate ligands. The first crown ether, 2,3,11,12-dibenzo-1,4,7,10,13,16-hexaoxacyclo-octadeca-2,11-diene, was obtained in 0.4% yield during an attempt to prepare a phenolic ligand from catechol and bis(2-chloroethyl)ether. This compound, which complexed with...

Complex formation between the silver(I) ion and monoazaand diaza-crown ethers has been studied in five polar, nonaqueous solvents using potentiometric techniques. The stability constants are spread over seven orders of magnitude, and the major contributor to this variation is the solvation of the silver(I) cation. The ring-size dependence of the stability constants is determined both by the cor...

Two series of homoleptic phenolate complexes with fluorinated aryloxide ligands A2[M(OAr)4] with M=Co2+ or Cu2+, OAr-=(OC6F5)- (OArF) or [3,5-OC6H3(CF3)2]- (OAr'), A+=K (18-crown-6)+, Tl+, Ph4P+, Et3HN+, or Me4N+ have been synthesized. Two related complexes with nonfluorinated phenoxide ligands have been synthesized and studied in comparison to the fluorinated aryloxides demonstrating the drama...

Complexes of the oxa-thia macrocycles [18]aneO4S2, [15]aneO3S2 and the oxa-selena macrocycle [18]aneO4Se2 (L) of types [MCl2(L)]FeCl4 (M = Sc or Y) were prepared from [ScCl3(thf)3] or [YCl2(THF)5][YCl4(THF)2] and the ligand in anhydrous MeCN, using FeCl3 as a chloride abstractor. The [MI2(L)]I, [LaI3(L)] and [LuI2(L)]I have been prepared from the ligands and the appropriate anhydrous metal trii...

Supramolecular cations formed by monoprotonated pyridazinium cations and cis-anti-cis-dicyclohexano[18]-crown-6 (DCH[18]-crown-6) or dibenzo[18]-crown-6 (DB[18]-crown-6) were introduced into [Ni(dmit)2]− salts (where dmit2− = 2-thione-1,3-dithiole-4,5-dithiolate). X-ray crystal structure analysis of (pyridazinium+)(DCH[18]-crown-6)[Ni(dmit)2]− (1) revealed a chair-type conformation of the DCH[1...