Molecular transformations of unsaturated thiacrown ethers.

Unsaturated thiacrown ethers with 15, 18, and 21 members were oxidized to sulfoxides by the reaction with m-CPBA. The reaction with t-BuOCl at -20 degrees C also afforded sulfoxides, whereas the reaction at room temperature yielded cis-trans isomerized compounds. The cis-trans isomerized compound was also obtained by the photochemical reaction or by the reaction with NCS and NCP.

Supramolecular complexes of La@C82 with unsaturated thiacrown ethers.

The paramagnetic La@C82-A(C2v) with unsaturated thiacrown ethers forms 1 : 1 host-guest complexes of [La@C82-A(C2v)]-[D]+ in solution as a result of electron transfer.

Unsaturated selenacrown ethers: synthesis, structure, and formation of silver complexes.

The unsaturated selenacrown ethers, (Z,Z,Z,Z,Z)-1,4,7,10,13-pentaselenacyclopentadeca-2,5,8,11,14-pentaene (15-US-5) (2), (Z,Z,Z,Z,Z,Z)-1,4,7,10,13,16-hexaselenacyclooctadeca-2,5,8,11,14,17-hexaene (18-US-6) (3), (Z,Z,Z,Z,Z,Z,Z)-1,4,7,10,13,16,19-heptaselenacycloheneicosa-2,5,8,11,14,17,20-heptaene (21-US-7) (4), (Z,Z,Z,Z,Z,Z,Z,Z)-1,4,7,10,13,16,19,22-octaselenacyclotetracosa-2,5,8,11,14,17,20,23-octaene (24-US-8) (5), and (Z,Z,Z,Z,Z,Z,Z,Z,Z)-1,4,7,10,13,16,19,22,25-nonaselenacycloheptacosa-2,5,8,11,14,17,20,23,26-nonaene (27-US-9) (6), were obtained together with 1,4-diselenin (1) by reacting sodium selenide with cis-dichloroethene in the presence of a phase-transfer catalyst. The crystal structures of 2-5 were determined by X-ray crystallographic analysis. The UV spectra of the selenacrown ethers showed absorption maximums in the range of 251-262 nm, which were assigned to n-->pi transitions.

Optically active seleninate esters: isolation, absolute configuration, racemization mechanism, and transformation into chiral selenoxide.

Optically active seleninate esters were obtained for the first time by chromatographic resolution on an optically active column. The absolute configurations of the optically active seleninate esters were determined by comparing their chiroptical properties with those of two analogous sulfinate esters, the absolute configuration of one of which is known and that of the other was determined by X-ray crystallographic analysis. The optically active seleninate esters were found to racemize in solution.

Optically active seleninamides: isolation, absolute configuration, and racemization mechanism.

Optically active seleninamides were obtained for the first time by chromatographic resolution on an optically active column. The absolute configurations of the optically active seleninamides were determined by comparing their chiroptical properties with those of analogous sulfinamides, the stereochemistry of which was determined by transformation into chiral sulfoxides of known configurations. The optically active seleninamides were found to racemize in solution.

Optical resolution and racemization mechanism of a tellurinic acid.

[reaction: see text] Optically active tellurinic acid was obtained for the first time by chromatographic resolution of racemic 2,4,6-triisopropylbenzenetellurinic acid (1) using a chiral column. Optically active tellurinic acid (+)-1 was stable toward racemization in hexane, although racemization occurred in hexane/2-propanol. The kinetic studies for the racemization, oxygen exchange reaction using H(2)(18)O, and theoretical studies clarified that the racemization of the optically active tellurinic acid in solution proceeds via a hypervalent tellurane formed by addition of water remaining in solvent.

Formation and structures of mercury complexes of 18-membered unsaturated and saturated thiacrown ethers.

The complexation of 18-membered unsaturated thiacrown ether, 18-UT-6, with 1 equiv of HgCl(2) in acetone afforded mercury complex Hg(II)(18-UT-6)Cl(2). The complexations of 18-membered saturated thiacrown ether, 18S6, with 1 equiv each of HgCl(2) and CdCl(2) in acetone afforded Hg(II)(18S6)Cl(2) and Cd(II)(18S6)Cl(2), respectively. The crystal structure of Hg(II)(18-UT-6)Cl(2) revealed that the mercury atom was inside the cavity of the macrocycle and the geometry around the mercury atom was an eight-coordinate hexagonal bipyramidal arrangement.

Synthesis and structures of 15- and 18-membered unsaturated selenacrown ethers and their complexation with silver trifluoroacetate.

The reaction of Na(2)Se with cis-dichloroethene yielded (Z,Z,Z,Z,Z)-1,4,7,10,13-pentaselenacyclopentadeca-2,5,8,11,14-pentaene (15-US-5) and (Z,Z,Z,Z,Z,Z)-1,4,7,10,13,16-hexaselenacyclooctadeca-2,5,8,11,14,17-hexaene (18-US-6). X-ray crystallographic analysis of 15-US-5 and 18-US-6 revealed an all-cis geometry around the carbon-carbon double bonds, with all of the selenium atoms located on one side of the respective ring planes. 15-US-5 and 18-US-6 were also found to be oxidized more easily than the corresponding sulfur analogues.

Silver complexes with unsaturated thiacrown ethers: inclusion behavior of conformationally restricted macrocycles.

The reactions of 18- and 21-membered unsaturated thiacrown ethers, 18-UT-6 and 21-UT-7, with CF(3)COOAg in acetone afforded novel silver(I) complexes Ag(I)(18-UT-6)(CF(3)COO) and Ag(I)(2)(21-UT-7)(CF(3)COO)(2), respectively. The crystal structure of Ag(I)(18-UT-6)(CF(3)COO) shows that the silver atom occupies the cavity of the 18-UT-6 and the geometry around the silver atom has a distorted five-coordinate square pyramidal arrangement. The crystal structure of Ag(I)(2)(21-UT-7)(CF(3)COO)(2) shows that the two silver atoms and all sulfur atoms are nearly coplanar and the two trifluoroacetate groups are located at the opposite sides of the plane.

Optical Resolution and Configurational Stability of Selenoxides Stabilized by Intramolecular Coordination.

2-((Dimethylamino)methyl)phenyl alkyl (or aryl) selenoxides, configurationally stabilized by intramolecular coordination of an amino group to the selenium atom, were optically resolved into their enantiomeric isomers by means of high-performance liquid chromatography using an optically active column packed with amylosecarbamate derivative/silica gel. This is the first example of the isolation of optically pure selenoxides without bulky substituents and also the first isolation of optically pure alkyl aryl selenoxides. The absolute configuration of the (-)-isomers could be assigned to be the S-form by comparison of their specific rotations, circular dichroism spectra, and behavior on the optically active column with those of the sulfur analogue, prepared by Andersen's method.

Syntheses and Peculiar Behavior in Solutions of Optically Active Telluronium Salts.

A diastereomeric (epimeric) mixture of ethylmethylphenyltelluronium (1S)-(+)-camphor-10-sulfonate (dia.-1) was optically resolved by fractional recrystallization into the diastereomerically pure isomers (R)(Te)-1 and (S)(Te)-1. The absolute configurations of the isomers were determined by the X-ray crystallographic analysis of (R)(Te)-1.