Strained silacycle-catalyzed asymmetric Diels-Alder cycloadditions: the first highly enantioselective silicon Lewis acid catalyst

The first highly enantioselective silicon Lewis acid catalyst for an asymmetric organic transformation has been developed. The catalyst derives its activity from the strain induced in the silicon center by virtue of being constrained in a five-membered ring. A simple tridentate ligand has been developed and the derived chlorosilane complex catalyzes the Diels-Alder cycloaddition of methacrolein and cyclopentadiene with 94% ee.     

The structure of monolayer SiO2 on Mo(1 1 2): A 2-D [Si-O-Si] network or isolated [SiO4] units?

In this letter, atomically resolved scanning tunneling microscopic (STM) images obtained from monolayer SiO₂/Mo(1 1 2) are presented. The results are consistent with a previously proposed structural model of isolated [SiO₄] units based on vibrational features observed by high-resolution electron energy loss spectroscopy (HREELS) and infrared reflection-absorption spectroscopy (IRAS), and oxygen species identified by ultra-violet photoemission spectroscopy (UPS). These results are inconsistent with a structural model that assumes a two-dimensional (2-D) [Si-O-Si] network. These data illustrate that a metal substrate, although coated with an oxide thin layer, can be directly imaged at the atomic-scale with STM.     

The chemisorption of pentacene on Si(0 0 1)-2 × 1

Adsorption structures of the pentacene (C₂₂H₁₄) molecule on the clean Si(0 0 1)-2 × 1 surface were investigated by scanning tunneling microscopy (STM) in conjunction with density functional theory calculations and STM image simulations. The pentacene molecules were found to adsorb on four major sites and four minor sites. The adsorption structures of the pentacene molecules at the four major sites were determined by comparison between the experimental and the simulated STM images. Three out of the four theoretically identified adsorption structures are different from the previously proposed adsorption structures. They involve six to eight Si-C covalent chemical bonds. The adsorption energies of the major four structures are calculated to be in the range 67-128 kcal/mol. It was also found that the pentacene molecule hardly hopped on the surface when applying pulse bias voltages on the molecule, but was mostly decomposed.     

Identity of defect causing nonideality in nearly ideal Au/n-Si Schottky barriers

We have proposed a mechanism of nonideality, i.e., the temperature dependence of the ideality factor, in nearly ideal Au/n-Si Schottky barriers. Because of the nature of metal-induced gap states, positively ionized defects close to the interface are considered to cause local lowering of the Schottky barrier height (SBH) due to downward bending of the energy band. These positively charged defects become neutralized in equilibrium with the Fermi level due to the band bending, when they are very close to the interface. However, because the SBH lowering disappears by the neutralization of donor, the energy level of donor with a usual energy level scheme rises above the Fermi level after the neutralization. This contradiction to the equilibrium neutralization is resolved by Si self-interstitial with a large negative-U property, which is generated by the fabrication process. The energy level of the donor estimated from the SBH lowering is in good agreement with that of theoretical calculation of Si self-interstitial. Thus, the defect is concluded to be the Si self-interstitial, which is distributed to more than 10 Å depth from the interface.     

New olefinic functionalized disilanes. Synthesis and NMR spectroscopical investigations

The new olefinic substituted aminodisilanes, which are obtained from the reaction of organometallic reagents with aminochlorodisilanes, are converted into the chlorodisilanes by equilibration reactions or treatment with HCI. The resulting olefinic functionalized disilanes are identified by means of ²⁹Si, ¹³C, ¹H NMR and GC MS measurements.     

Current methods for site-directed structure generation

Summary There has been a rapid growth of interest in techniques for site-directed drug design, fuelled by the increasing availability of structural models of proteins of therapeutic importance, and by studies reported in the literature showing that potent chemical leads can be obtained by these techniques. Structure generation programs offer the prospect of discovering highly original lead structures from novel chemical families. Due to the fact that this technique is more-or-less still in its infancy, there are no case studies available that demonstrate the use of structure generation programs for site-directed drug design. Such programs were first proposed in 1986, and became commercially available in early 1992. They have shown their ability to reproduce, or suggest reasonable alternatives for, ligands in well-defined binding sites. This brief review will discuss the recent advances that have been made in the field of site-directed structure generation.     

Recent developments in polymeric charge transfer complexes

The recent literature on polymeric charge transfer complexes is reviewed with emphasis on the author's own work. After a definition of the area and a survey of investigations on the spatial arrangement of donor and acceptor sites in the solid state, a variety of applications of these complexes is presented. Electrically conductive polymers are excluded. These applications are: compatibilization of polymer blends, liquid crystalline supramolecular organization, new developments in photo-conductivity, electroluminescence, nonlinear optical properties, photorefractivity and reversible optical storage.     

Flaked capillary columns with crown ether complexes for gas-liquid chromatography

Flaked capillary columns with an OV-101/CE-Na{in3}PO{in4} hydrophobic-hydrophilic sorbent have been suggested. This sorbent provides for the analysis of polar and nonpolar substances, including amines and aminoalcohols, in aqueous and organic solvents. The efficiency of new columns was demonstrated for the analysis of 25 organic substances of various classes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2169–2173, December, 1994.The work was financially supported by the Russian Foundation for Basic Research, Project No. 93-03-4969.     

Thermal decomposition of hexamminecobalt(III) chloride

The results of comparative thermal analysis (TG-DTG-DTA-DSC) of the thermal decomposition of hexamminecobalt(III) chloride in air atmosphere are reported. The kinetics and mechanism of the thermal decomposition, the process enthalpy and the variation in specific thermal capacity of the solid product reaction with temperature were determined.     

Metal–Nitrosyl complexes as a source of new vasodilators: Strategies derived from systematic chemistry and nitrosyl ligand reactivity

A series of nitrosyl complexes of empirical formula K_n[M(CN)₅NO], where M = V, Cr, Mn and Co and n = 3, or M = Mo and n = 4, have been prepared which are notional analogues of the widely used vasodilator sodium nitroprusside. Their reactivity towards common nucleophiles (OH^?, NH₂R, NHR₂, HS^? and RS^?), acid and photolysis has been investigated to elucidate the desired properties required of new metal nitrosyls which may have some potential as new non-cyanide-based vasodilators.