Ru-Catalyzed asymmetric hydrogenation of alpha-ketoesters with CeCl3.7H2O as additive

[reaction: see text] An efficient asymmetric hydrogenation of alpha-ketoesters is reported with use of a catalyst prepared from [Ru((S)-3)(benzene)Cl]Cl and CeCl(3).7H(2)O. Alpha-hydroxy esters are obtained in up to 96% ee. The addition of CeCl(3).7H(2)O not only improves the enantioselectivity, but also enhances the stability of the catalyst. As a result, the hydrogenation of methyl benzoylformate affords the product with 92% ee with a substrate/catalyst ratio of 10 000. Hydrolysis of 2 provides the final compound with 83% yield at 99% ee after a single recrystallization from 1,2-dichloroethylene.     

Luminescence centers in porous silicon

Photoluminescence studies on porous silicon show that there are luminescence centers present in the surface states. By taking photoluminescence spectra of porous silicon with respect to temperature, a distinct peak can be observed in the temperature range 100–150 K. Both linear and nonlinear relationships were observed between excitation laser power and the photoluminescence intensity within this temperature range. In addition, there was a tendency for the photoluminescence peak to red shift at low temperature as well as at low excitation power. This is interpreted as indicating that the lower energy transition becomes dominant at low temperature and excitation power. The presence of these luminescence centers can be explained in terms of porous silicon as a mixture of silicon clusters and wires in which quantum confinement along with surface passivation would cause a mixing of andX band structure between the surface states and the bulk. This mixing would allow the formation of luminescence centers.     

μ-phenoxo-bridged binuclear copper(II) complexes

Summary Two -phenoxo-bridged binuclear copper(II) complexes, [Fsal(GG)₂Cu₂Cl₃]·H₂O (1) containing an exogenous chloride-bridge and [Fsal(GG)₂Cu₂(OH)](ClO₄)₂·H₂O (2) containing an exogenous hydroxide-bridge, where {Fsal(GG)₂ = 2,6-bis[N-(acetylglycine)-imino-methylene]-4-methylphenol}, were synthesized. The complexes were characterized be several spectroscopic methods. According to variable temperature magnetic susceptibility measurements (4–300 K), the hydroxide-bridged complex (2) has a weak antiferromagnetic spin exchange integral (J =- 23.6 cm), while the chloride complex (1) has an unusual weak ferromagnetic spin exchange integral (J = + 30.9 cm); both complexes have similar optical spectra in the aqueous solutions.     

Hydrolysis of 2-aminoethanethiolsulfate ions

The kinetics of the acid catalyzed hydrolysis of 2-aminoethanethiolsulfate (AETS) ions were investigated. The dependence of the hydrolysis rate constant on acidity and temperature was determined. The hydrolysis rate equation can be expressed as where H_o is the Hammett acidity function. The rate constant, k, can be expressed as The pK_a's for the compound were measured and literature value of pK_a was found to be in error. The values determined in this study are pK_a1 < ?0.5 and pK_a2 = 9.1 ± 0.1. General acid catalysis of the hydrolysis reaction was found not to proceed to a significant degree. © 1994 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

A five-channel grating spectrometer for millimeter-waves

A five-channel grating spectrometer for use in millimeter wave band (25100GHz) is described with its design theory of optical path, and measured results of insertion loss and resolving power.     

Synthesis and Structureof［（C_2H_5）_4N］［Mo_3（μ_3－O）（μ－Cl）_3（μ－CH_3CH_2COO）_3Cl_3］

ＳｙｎｔｈｅｓｉｓａｎｄＳｔｒｕｃｔｕｒｅｏｆ［（Ｃ_２Ｈ_５）_４Ｎ］［Ｍｏ_３（μ_３－Ｏ）（μ－Ｃｌ）_３（μ－ＣＨ_３ＣＨ_２ＣＯＯ）_３Ｃｌ_３］ＺｈｕａｎｇＨｏｎｇ－Ｈｕｉ；ＷｕＤｉｎｇ－Ｍｉｎｇ；ＨｕａｎｇＪｉａｎ－Ｑｕａｎ；ＨｕａｎｇＪｉｎ－Ｌ...     

气相色谱中测定死时间的Grobler－Balizs法和Ambrus法的比较

经理论推导和实验数据验证，证明测定死时间的Ｇｒｏｂｌｅｒ－Ｂａｌｉｚｓ法和Ａｍｂｒｕｓ法是同一的。     

An order-disorder transition in Sr2IrD5: Evidence for square pyramidal IrD5 units from powder neutron diffraction data

Neutron diffraction data have been collected on a powdered sample of Sr₂IrD₅ over a range of temperatures. The compound, which is cubic at room temperature, has been found to exhibit a gradual transformation to a tetragonal phase in the temperature range 200-140 K. As a result of the transition, deuterium atoms which randomly occupy sixfold positions in the cubic phase, become tetragonally ordered. A small fraction of the cubic phase remained untransformed at 4.2 K. Both the cubic and tetragonal structures are consistent with square pyramidal IrD₅ units with average Ir---D distances of 1.714 and 1.718 Å, respectively. Agreement factors, R₁, for the two structural analyses are 3.44 and 4.94%.     

Statistical radical copolymerization of styrene and methyl methacrylate in a room temperature ionic liquid

Use of a room temperature ionic liquid as the medium for conventional free radical copolymerization of styrene and methyl methacrylate resulted in reactivity ratios that were significantly different from those obtained in conventional organic solvents or in bulk, demonstrating that polymerization in this alternative medium offers potential to create copolymers having new monomer sequences.