Chloride ion promoted nucleophilic pentafluorophenylation of imines

Nucleophilic addition of the pentafluorophenyl group from (C₆F₅)₃SiF to non-activated imines affording α-C₆F₅-substituted secondary amines in high yield has been described. The reaction proceeds via simultaneous activation of imines and the silane reagent by means of a proton and chloride ion, respectively.     

Strong intramolecular secondary si.N bonds in trifluorosilylhydrazines

The simple silylhydrazines F(3)SiN(Me)NMe(2) (1), F(2)Si(N(Me)NMe(2))(2) (2), and F(3)SiN(SiMe(3))NMe(2) (3) have been prepared by reaction of SiF(4) with LiN(Me)NMe(2) and LiN(SiMe(3))NMe(2), while F(3)SiN(SnMe(3))NMe(2) (4) was prepared from SiF(4) and (Me(3)Sn)(2)NNMe(2) (5). The compounds were characterized by gas-phase IR and multinuclear NMR spectroscopy ((1)H, (13)C, (14/15)N, (19)F, (29)Si, (119)Sn), as well as by mass spectrometry. The crystal structures of compounds 1-5 were determined by X-ray crystallography. The structures of free molecules 1 and 3 were determined by gas-phase electron diffraction. The structures of 1, 2, and 4 were also determined by ab initio calculations at the MP2/6-311+G** level of theory. These structural studies constitute the first experimental proof for the presence of strong Si.N beta-donor-acceptor bonds between the SiF(3) and geminal NMe(2) groups in silylhydrazines. The strength of these non-classical Si.N interactions is strongly dependent on the nature of the substituent at the alpha-nitrogen atom of the SiNN unit, and has the order 3>4>1. The valence angles at these extremely deformed alpha-nitrogen atoms, and the Si.N distances are (crystal/gas): 1 104.2(1)/106.5(4) degrees, 2.438(1)/2.510(6) A; 3 83.6(1)/84.9(4) degrees, 2.102(1)/2.135(9) A; 4 89.6(1) degrees, 2.204(2) A.     

Double Pore Silica Gel Monolith Applied to Liquid Chromatography

Silica gels retaining double pore structure in the size ranges of micrometer and nanometer have been applied to the rod-shaped monolithic column for liquid chromatography. The macropore structure was designed by controlling the phase separation process induced by the hydrolysis and polycondensation of alkoxysilane, whereas the mesopore structure was tailored by the solvent exchange treatments on wet gels. The size exclusion chromatograms on polystyrene standards exhibited almost similar features for octadecyl-modified rod and conventional packed beads columns. The dependence of plate height on the velocity of mobile phase determined for amylbenzene was by far weaker in the rod column than in the packed beads column, suggesting that additional geometrical factors should be considered in describing the separation mechanism in the rod column.     

Reactions of salicylaldehyde with tris(pentaf luorophenyl)silanes and secondary amines

Reactions of tris(pentafluorophenyl)silanes RSi(C₆F₅)₃ with salicylaldehyde and secondary amines were studied. The reactions afforded α-pentafluorophenyl-substituted amines. Silanes RSi(C₆F₅)₃ (R = Me, Ph, C₆F₅, CH₂CH=CH₂, and CH=CH₂) were found to be efficient reagents for transfer of the C₆F₅ group to the iminium cation generated from salicylaldehyde and amine. However, tris(pentafluorophenyl)phenylethynyl-and tris(pentafluorophenyl)silanes were not able to serve as a source of a fluorinated substituent because of competitive transfer of acetylenide fragment or hydride. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 498–503, March, 2006.     

硅表面嫁接有机单分子膜的研究近况

由于在微电子、化学 /生物化学传感器、纳米技术及太阳能等领域具有潜在的应用价值 ,通过 Si— C键在硅表面上直接嫁接有机单分子膜 ,已成为近几年新开展的研究热点 .对这一研究领域进行了概要综述     

失效原子力显微镜硅针尖再生

原子力显微镜的传统商品硅针尖在使用过程中极易因磨损而失效，本文研究了一种在实验室条件下简易可行的回收利用失效硅针尖的方法。在原子力显微镜的敲击模式下使用曲率半径大于100 nm的失效硅针尖对生长单壁碳纳米管的样品表面进行扫描，把样品表面的单壁碳纳米管管束粘接到硅针尖上，可制得直径在5～20 nm的碳纳米管针尖。实验对碳纳米管针尖和新的商品硅针尖进行了成像对比，所制备的碳纳米管针尖不仅在成像分辨率而且在成像稳定性上都优于新的商品硅针尖。     

Surface cavities produced by high‐dose nitrogen ion implantation into silicon

Nitrogen ion implantation (24 keV, 4.6 × 10¹⁷ cm^?2) into (100) a p‐type silicon wafer material and a subsequent electron beam annealing at 1100 °C for 15 s under high vacuum conditions leads to the formation of an uneven surface in the implanted region caused by nitrogen bubbles beneath the surface. Annealing at 1200 °C for 300 s results in surface cavities with a mean diameter of 350 nm and a surface coverage of 3–4% and an average depth of ～60 nm. Nuclear reaction analysis reveals that the nitrogen concentration in the as‐implanted state exceeds 57 at%, the value of stoichiometric Si₃N₄. Annealing at 1100 °C for 15 s slightly reduces the nitrogen peak concentration, whereas annealing at 1200 °C for 300 s induces a significant alteration to the shape of the nitrogen depth profile coupled with the lowering of the concentration close to the stoichiometry of Si₃N₄. The results present a new method of producing sub‐micrometre cavities embedded in a thin silicon nitride film on wafer silicon which may lead to novel micro‐electronic and biotechnology applications. Copyright © 2007 John Wiley & Sons, Ltd.     

高多孔度多孔硅自支撑膜的制备与表征

发光多孔硅由于在光电子学方面的应用前景而引起人们极大的关注[1]．最近多孔硅发光二极管的研究方面取得了重大进展[2]。但是，有关多孔硅的发光机制仍然存在着争论[1，3，4]，利由于消除了单晶硅衬底的影响，对脱离了硅衬底的多孔硅自支撑膜能够进行普通多孔硅所不能进行的一     

Nitrido-silicate. II [1]. Hochtemperatur-Synthesen und Kristallstrukturen von Sr2Si5N8 und Ba2Si5N8

Nitrido-Silicates. II. High Temperature Syntheses and Crystal Structures of Sr₂Si₅N₈ and Ba₂Si₅N₈ Pure Sr₂Si₅N₈ and Ba₂Si₅N₈ were obtained by reaction of silicon diimide with metallic strontium and barium, respectively. The reactions have been carried out under nitrogen atmosphere in a specially developed high-frequency furnace at temperatures between 1 550 and 1 650°C. Sr₂Si₅N₈ (Pmn2₁, a = 571.0(2), b = 682.2(2), c = 934.1(2) pm, Z = 2, R = 0.037, wR = 0.021) and Ba₂Si₅N₈ (Pmn2₁, a = 578.3(2), b = 695.9(2), c = 939.1(2) pm, Z = 2, R = 0.022, wR = 0.018) are isotypic and contain M²⁺ ions as well as a three-dimensional covalent network structure of corner-sharing SiN₄ tetrahedra. Two sorts of N occur with molar ratio 1 : 1 which are bonded to two and three Si, respectively. Predominantly, the N which are bonded to two Si belong to the coordination spheres of the M²⁺ ions.