Benzoyl(acetylacetonato)nickel(II) complexes containing tertiary phosphine ligands. Their synthesis,dynamic behavior in solution,and decarbonylation

Carbon monoxide is readily inserted into the phenyl—nickel bond of PhNi(acac)(PR₃)_n to give benzoylnickel complexes, PhCONi(acac)PR₃ (R = Ph, Et, cyclo-C₆H₁₁), which were characterized by elemental analysis, IR and NMR spectroscopy, as well as chemical reactions. The reactions of the benzoylnickel complexes with methyl iodide and alcohols give acetophenone and corresponding benzoates, respectively, accompanied by some decomposition reactions. The solid benzoylnickel complexes when heated at elevated temperatures are decarbonylated and biphenyl, benzophenone and carbon monoxide are liberated. The dynamic behavior of the acac ligand in acetone solution was studied and the activation parameters for the acac exchange reactions were obtained. The decarbonylation reaction of the benzoyl complex PhCONi(acac)PPh₃ in acetone was studied by NMR, and found to be first order in the benzoylnickel complex.     

Catalytic asymmetric desymmetrization of cyclic meso-1,3- and 1,4-diols by a phosphinite derivative of quinidine

Asymmetric monobenzoylation reactions of cyclic meso-1,3- and 1,4-diols were catalyzed by a phosphinite derivative of quinidine to afford the corresponding monobenzoylated diol with good yield and enantioselectivity. [reaction: see text]     

Self-assembly of flexible supramolecular metallacyclic ensembles: structures and adsorption properties of their nanoporous crystalline frameworks

The syntheses, structures, and N2 adsorption properties of six new supramolecular metallacycles are reported. Flexible ditopic linkers, 1-4, with systematically varied lengths and conformational degrees of freedom were synthesized utilizing ester linkages. They were used in combination with (dppp)M(OTf)2, where M = Pt(II) and Pd(II), and cis-(Me3P)2Pt(OTf)2 to form flexible supramolecular metallacycles 5-10 in 88-98% isolated yields. Their structures were characterized via multinuclear NMR and X-ray crystallography. The metallacycles stack to form porous structures in the crystalline state. The pore dimensions depend on both the phosphorus ligands attached to the metals and the flexible linkers. Adsorption studies on the porous materials show that 5a, 6, 8, and 9 held 11.7, 16.5, 5.7, and 6.8 cm3/g STP of N2 at 77 K, respectively. A guest-exchange study with nitromethane and toluene reveals that the nanopore in 5 is flexible, a property which was transferred from the linker to the supramolecular structure in the solid state.     

Isolation, characterization, and theoretical study of La2@C78

A new metallofullerene, La2@C78, has been synthesized by DC arc discharge method, isolated by high-performance liquid chromatography, and characterized by laser desorption time-of-flight mass spectrometry, UV-vis-NIR absorption, differential pulse voltammetry, 13C NMR spectroscopy, and theoretical calculations. The La2@C78/CS2 solution is dark violet and presents several characteristic absorption features at 647, 561, 533, and 386 nm, with an onset around 1000 nm. With respect to empty D3-C78, the capability of La2@C78 as an electron acceptor or donor is stronger. Addition of 1,1,2,2-tetrakis(2,4,6-trimethylphenyl)-1,2-disirane to La2@C78 photochemically, as well as thermally, affords bis- and mono-adducts. Theoretical studies and 13C NMR spectroscopic analysis of La2@C78 indicate that it possesses a D3h-C78 cage (78:5).     

Phenotyping of erythrocyte acid phosphatase and esterase D by high field strength isoelectric focusing on cellulose acetate membrane

Phenotyping of erythrocyte acid phosphatase (EAP) and esterase D (ESD) by cellulose acetate membrane isoelectric focusing (CAM-IEF) under a nonequilibrium condition is described. In an attempt to improve the method of CAM-IEF, we shortened the electrode distance to provide a higher field strength at a given (low) voltage. Various carrier ampholytes for EAP typing and various chemical separators for ESD typing were also tested. Good separations were obtained after 30 min IEF for EAP typing and 25 min for ESD typing. When applied to blood stains and stored for various periods at room temperature, the stains up to 8 months old could still be phenotyped for EAP and those up to 4 weeks old for ESD. CAM-IEF is suitable for routine forensic work of EAP and ESD phenotyping.     

Plutonium isotopes and 137Cs in Dolon settlement near the Semipalatinsk Nuclear Test Site: About 50 years after the first nuclear weapon testing

Recent controversies concerning the radiation doses for populations living in the village of Dolon due to the nuclear explosions carried out at the Semipalatinsk Nuclear Test Site (SNTS) have encouraged us to evaluate in more detail the levels and distributions of residual long-lived radionuclides¹³⁷Cs and Pu isotopes (²³⁸Pu,^239,240Pu) in soils within the village. Soil core samples up to a depth of about 30 cm and/or 100 cm were collected at 25 sites and subjected to analysis of ¹³⁷Cs and Pu isotopes. The inventories of ¹³⁷Cs and ^239,240Pu were found to be in the wide range of 790-10,310 and 530-14,320 Bq/m², respectively. Sequential leaching of Pu from the soil showed that more than ca. 80% of the ^239,240Pu was not leached by hot digestion with conc. HNO³ + H₂O₂, indicating the presence of Pu associated with fused silicates. Further, the presence of hot-particles from the Pu contaminants by a-track radiography technique using CR-39 polycarbonate was confirmed in the soil, even at present, after about 50 years from the first nuclear weapon testing. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation of substituted benzoyltrimethylsilanes by the palladium-catalyzed silylation of substituted benzoyl chlorides with hexamethyldisilane

A direct preparative route to benzoyltrimethylsilane has been found by the reaction of benzoyl chloride with hexamethyldisilane in the presence of a specified palladium(II) complex as catalyst.