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. ORTEP drawing of Hg(II)(18S6)Cl(2) revealed the existence of the mercury atom outside the cavity of the ring, as well as a polymeric chain structure. (1)H NMR study of Hg(II)(18-UT-6)Cl(2) in acetone-d(6) indicated that the interconversion between free 18-UT-6 and pure complex was slower than the NMR time scale. The titration experiment by (1)H NMR revealed that 18-UT-6 had inclusion selectivity for the number of mercury atoms. The electrochemical behavior of complexes Hg(II)(18-UT-6)Cl(2) and Hg(II)(18S6)Cl(2) was also examined.     

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. Kinetic studies of the racemization, the oxygen exchange reaction with H(2)(18)O, and theoretical studies clarified that the racemization of the optically active seleninate esters in solution proceeded via an achiral hypervalent selenurane intermediate that was formed by the reaction with water. The reaction of the optically active seleninate ester and the sulfinate ester having bulky substituents with Grignard reagents was found to proceed with the retention of stereochemistry to give an optically active selenoxide and sulfoxides, respectively.     

Catalytic activity of Cu(II)–poly(vinyl alcohol) complex for decomposition of hydrogen peroxide

Decomposition of hydrogen peroxide was examined was examined by using Cu(II)–poly(vinyl alcohol) (PVA) as catalyst. The rates of decomposition were measured. Electronic spectra and infrared spectra of Cu(II)–PVA complex systems were determined at various stages of decomposition. Effect of addition of various amines to the Cu(II)–PVA system on catalytic action was considered. The relation between the initial rate and the initial concentration of hydrogen peroxide varied in accordance with the rate expression of Michaelis-Menten type. Cu(II)–PVA complex was found to have a large catalytic activity, while the polymeric PVA ligand and copper(II) ion exhibited less activity than Cu(II)–PVA complex. For hydrogen peroxide decomposition, Cu(II)–PVA complex showed catalytic activity when a stable complex of planar structure formed, while many other polymer complexes reported by other authors showed the catalytic activity when they were in unstable complex forms. An amine substituent has a critical influence on the rate of hydrogen peroxide decomposition. The mechanism in the first step of reaction for hydrogen peroxide decomposition is discussed.     

First Isolation and Stereochemistry of Optically Active Telluroxides

Optically active telluroxides 1 and 2 were isolated for the first time by means of medium-pressure liquid chromatography using an optically active column. Absolute configuration of the telluroxides (+)-1 and (+)-2 was determined to be R based on their specific rotations and circular dichroism spectra. The configurational lability and mechanism for racemization via an achiral hydrate were clarified by kinetic study and isotope tracer experiment.     

Possible copper based superconductors by the combination of blocking and mediating layers

Copper based high temperature superconductors are composed of Cu–O₂ sheets in combination with thin atomic mediating layers and thick blocking layers which mediate and intercept interactions between Cu–O₂ sheets, respectively. New possible superconductors can be designed by the stacking of the Cu–O₂ sheets along with the periodic insertion of the mediating layers and different kinds of blocking layers. Characteristics of the blocking layers, and formulas of possible superconductors are given for one, two and three Cu–O₂ sheets compounds.     

A novel UV-sensitive photopolymerization system with microgel matrix

A series of crosslinked microgels with quaternary ammonium ions on the surface was prepared by quaternization with N,N-dimethylbenzylamine in the presence of microgel particles prepared by emulsion copolymerization of styrene (St), chloromethylstyrene (CMS) and divinylbenzene (DVB). Microgels with diameters in the range of 15–100 nm were successfully dispersed in organic solvents such as 2-methoxyethanol and 2-ethoxyethanol without an emulsifier. A photosensitive layer was formed by coating a photosensitive solution on a grained aluminum plate. The solution was comprised of the microgels, the multifunctional monomer and standard ultraviolet (UV) photoinitiators, such as 2,4-diethyl thioxanthone (DETX)/ethyl p-di-ethylaminobenzoate (EPA). This gave a heterogeneous photosensitive layer which produced good polymer patterns after exposure to UV light followed by development in tap water. A typical polymer layer, consisting of the microgels (poly(styrene-co-N,N-dimethylbenzylvinyl-benzylammonium chloride-co-divinylbenzene)), DETX/EPA, and the multifunctional acrylate monomers, exhibited photosensitivity of 0.06 mJ/cm² for UV light. This sensitivity is much higher than the homogeneous photopolymerization system with an analogous composition.     

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. Kinetic studies of the racemization and theoretical studies clarified that the racemization of the optically active seleninamides in solution proceeds via hypervalent hydrates formed by the reaction with water.     

Synthesis and Thermal Reaction of 1,3-Bis(alkylseleno)allenes

Reactions of Ph(2)C(3) dianion, prepared from 1,3-diphenylpropyne and n-butyllithium, with dimethyl diselenide and benzylselenocyanate yielded 1,3-bis(methylseleno)-1,3-diphenylpropadiene and 1,3-bis(benzylseleno)-1,3-diphenylpropadiene, respectively, and the reaction with a mixture of dimethyl diselenide and benzylselenocyanate gave 1-benzylseleno-3-methylseleno-1,3-diphenylpropadiene together with the symmetric products. Thermal reactions of the 1,3-bis(alkylseleno)allenes afforded (E)- and (Z)-1,3,4,6-tetraphenyl-3-hexene-1,5-diynes along with compounds derived from cyclic dimer of the allene or diselenide via radical pathway.