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81.
The preparation of SiH-containing silylphosphines from SiH-containing chlorosilanes is successful by using an excess of chlorosilans. Chemical shift data and coupling constants of the compounds HxSi[P(C2H5)2]4?x and (CH3)xSi[P(C2H5)2]4?x are communicated and compared with those of HxSiX4?x and (CH3)xSiX4?x (X = halogen or H). 相似文献
82.
Controlled anodic dissolution of copper in a separate generator cell yields well-defined concentrations of catalyst, depending on the voltage applied. This adjustable generation of copper catalyst makes it possible to determine iron over a wide range of concentration (10–1500 μg Fe3+ ml-1) via the iron(III)—thiosulphate reaction. By the copper(II)-catalyzed hydrogen peroxide—hydroquinone reaction, EDTA can be determined as an inhibitor (0.5–5 μg ml-1) and cadmium(II) as a reactivator (1–10 μg ml-1). As zinc(II) forms complexes with 2,2'-bipyridine, which activates copper in this reaction, it can be determined (5–50 μg Zn2+ ml-1) by measuring the decrease in activation. The electrogeneration of silver ion as a catalyst is also described. The sulphanilic acid—peroxodisulphate reaction is catalyzed by silver(I), which is again activated by 2,2'-bipyridine. Zinc(II) can be determined (0.29–2.9 mg Zn2+ ml-1) by the same principle as in the copper(II)-catalyzed reaction. 相似文献
83.
Formation of Organosilicon Compounds. LVI. Reactions of Si- and C-Chlorinated 1,3,5-Trisilapentanes with CH3MgCl (Cl3Si? CCl2)2SiCl2 (1) reacts with an excess of meMgCl (me = CH3) forming me3Si? C?C? Sime3 (2), Sime4, H2C?C(Sime3)[CH(Sime3)2] (3) as main products and (me3Si)2C? CH(Sime3) and as by-products. The cleavage reaction of (1) to (2) and (3) does not occur when the meMgCl-concentration is lowered. The reaction is started by the formation of a GRIGNARD reagent at a CCl-group in compound (1). Cl3Si? CCl2? SiCl2? CH2? SiCl3 forms with ; me3Si? CCl2? SiCl2? CHCl? SiCl3 forms (me3Si)2C?CH(Sime3). A reaction sequence is given. 相似文献
84.
Formation and Reaction of P-functional Phosphanes The reaction of (me3Si)2PLi · 2 THF a (me = CH3) with PCl3 b at ?78°C via the intermediate (me3Si)2P? PCl2 1 yields [(me3Si)2P]2PCl 2 and [(me3Si)2P]2P? P(Sime3)2 3 . By addition of me3CLi c to the reaction mixture of a and b (molar ratio a:b:c (molar ratio a:b:c = 1:1:1) at ?60°C, 2 is formed as a main product, which reacts on to yield [(me3Si)2P]2PH 4 (white crystals, mp = 73°C). By reactions of a:b:c in a molar ratio of 1:1:2 the cyclotetraphosphane (me3C)3 (me3Si)P4 7 is accessible, and the additional formation of (me3Si)2PLi · 2 THF, (me3Si)3P and Li3P7 · 3 THF 13 was detected. Warming (me3Si)2P? PCl(Cme3) 5 to 20°C produces cis- and trans-cyclotetraphosphanes (me3Si)2(me3C)2P4. By running the reaction of a and b at ?78°C and adding me3CLi only after 24 h, additionally to (me3Si)2P? PH Cme3) and (me3Si)3P also (me3Si)2P? P(Cme3)? P(Cme3)? P (Sime3)2 is obtained, which is formed by metallation of (me3Si)2P? PCl(Cme3) with me3CLi and by further reaction of the intermediate (me3Si)2P? PLi(Cme3) with (me3Si)2P? PCl(Cme3). The reaction of (me3Si3)P with PCl3 at ?78°C only yields (me3Si)2P? PCl2 1 and me3SiCl. On addition of me3CLi (?78°C, molar ratio = 1:1:1) preferrably 2 and (me3Si)2P? PCl(Cme3) are formed, whereas after warming the mixture to 20°C, 4 and (me3Si)2P? PH(Cme3) are found to be the main products. These reactions are induced by the cleavage of 1 by means of me3CLi, and by the formation of (me3Si)2PLi and me3C? PCl2. 相似文献
85.
Miriam Rosenbaum Uwe Schröder Fritz Scholz 《Journal of Solid State Electrochemistry》2006,10(10):872-878
In this communication, we discuss the electro-oxidation of the fermentation products formate and ethanol at platinum black modified electrodes under microbial fuel cell conditions, i.e., at neutral pH, room temperature, and in microbial culture solutions. The electrocatalytic oxidation was studied using cyclic voltammetry, chronoamperometry, and potentiostatic coulometry. Current densities up to 6 mA cm−2 at 0.2 V oxidation potential and 97% coulombic efficiency were observed for the electro-oxidation of 100 mM solutions of formate in pH 7 buffer solution. Electrode deactivation could be successfully prevented using an oxidative potential reactivation procedure. Polymer coating, however, fully stopped the formate oxidation. As expected, the electro-oxidation of ethanol was less efficient—with a limiting current density being 600 μA cm−2.Dedicated to Professor Dr. Alan M. Bond on the occasion of this 60th birthday. 相似文献
86.
Fritz SE Martin SM Frisbie CD Ward MD Toney MF 《Journal of the American Chemical Society》2004,126(13):4084-4085
Grazing incidence X-ray diffraction reveals that a pentacene monolayer, grown on an amorphous SiO2 substrate that is commonly used as a dielectric layer in organic thin film transistors (OTFTs), is crystalline. A preliminary energy-minimized model of the monolayer, based on the GIXD data, reveals that the pentacene molecules adopt a herringbone arrangement with their long axes tilted slightly from the substrate normal. Although this arrangement resembles the general packing features of the (001) layer in single crystals of bulk pentacene, the monolayer lattice parameters and crystal structure differ from those of the bulk. Because carrier transport in pentacene OTFTs is presumed to occur in the semiconductor layers near the dielectric interface, the discovery of a crystalline monolayer structure on amorphous SiO2 has important implications for transport in OTFTs. 相似文献
87.
The discovery and design of new materials with competitive optical frequency conversion efficiencies can accelerate the development of scalable photonic quantum technologies. Metal–organic framework (MOF) crystals without inversion symmetry have shown potential for these applications, given their nonlinear optical properties and the combinatorial number of possibilities for MOF self-assembly. In order to accelerate the discovery of MOF materials for quantum optical technologies, scalable computational assessment tools are needed. We develop a multi-scale methodology to study the wavefunction of entangled photon pairs generated by selected non-centrosymmetric MOF crystals via spontaneous parametric down-conversion (SPDC). Starting from an optimized crystal structure, we predict the shape of the G(2) intensity correlation function for coincidence detection of the entangled pairs, produced under conditions of collinear type-I phase matching. The effective nonlinearities and photon pair correlation times obtained are comparable to those available with inorganic crystal standards. Our work thus provides fundamental insights into the structure–property relationships for entangled photon generation with metal–organic frameworks, paving the way for the automated discovery of molecular materials for optical quantum technology.The discovery and design of new materials with competitive optical frequency conversion efficiencies can accelerate the development of scalable photonic quantum technologies. 相似文献
88.
Johann-Peter Melder Klaus Weber Andreas Weiler Emmerich Sackers Hans Fritz Dieter Hunkler Horst Prinzbach 《Research on Chemical Intermediates》1996,22(7):667-702
Methodological alternatives for the preparation of highly strained, highly pyramidalized dodecahedrene 2 (Estr=87.3 kcal mol?1; ?=43.5°, MM2) and 1,16-dodecahedradiene 3 (Estr=105.3 kcal mol?1; ?=42.9°, MM2) have been explored, protection/deprotection strategies have been tested—with the eye on their utilization for the generation of higher unsaturated dodecahedranes (e.g. 1,4, 16-triene 4, 1,4,10 (14),16-tetraene 5). For the acquisition of preparative quantities of monoene 2 the “P2F” catalyzed cis-β-elimination in bromododecahedrane, of diene 3 the FVP fragmentation of a “twofold protected” precursor (bis-furan adduct) have become the protocols of choice, which both profit from the recent synthetic advances along the pagodane → dodecahedrane scheme. Because of unusually effective steric protection the highly tilted C=C double bonds of 2 (λmax (CH3CN) = 254 nm, ν C=C = 1658 cm?1, δC=C = 164.4) and 3 (δC=C = 170.5) enter into thermal stabilization pathways (dimerization, oligomerization) only at higher temperatures (for 2 ca. 50% consumption after 5 h at 100°C in a 3·10?3 molar toluene solution); extreme sensitivity to oxygen is primarily attributed to kinetically and thermodynamically promoted allylic hydrogen abstraction. 相似文献
89.
T. A. Furstch L. T. Taylor T. W. Fritz G. Fortner E. Khor 《Journal of polymer science. Part A, Polymer chemistry》1982,20(5):1287-1298
Five polyimide films prepared from 3,3′,4,4′-benzophenone tetracarboxylic acid'dianhydride (BTDA) and diamines, 4,4′-oxydianiline (ODA), 3,3′-diaminobenzophenone (DABP), or 3,3′-diaminodiphenylcarbinol (DADPC) and doped with Li2PdCl4 (LTP) or Pd[(CH3)2S]2Cl2 (PDS) were selected for a detailed x-ray photoelectron spectroscopic (XPS) study to determine the oxidation state of palladium and the relative distribution of this and other elements in these films, especially as they relate to electrical resistivity. XPS shows that Pd in the films is present as a mixture of zero and +2 valence states. Films that contain lithium as part of the dopant all show that metal is present as Li+ and Li2O, a fact that may have a bearing on film electrical properties. An Auger electron spectroscopic (AES) or XPS profiling was performed on two of the electrically conductive films. A film doped with PDS reveals a majority of palladium at the surface as Pd(0) and much smaller amounts in film bulk as a mixture of Pd(0) and Pd(II). Film behavior is similar to a metal-vapor deposited film. An LTP doped film, by contrast, exhibits a homogeneous composition with a mixture of Pd(0) and Pd(II). These studies support others that use chemical etching on the film surfaces. Scanning electron microscopy (SEM) has been used to provide surface evaluations. 相似文献
90.
Synthesis and Properties of Partially Silylated Tri- and Tetraphosphanes. Reaction of Lithiated Diphosphanes with Chlorophosphanes The reactions of Li(Me3Si)P? P(SiMe3)(CMe3) 1 , Li(Me3Si)P? P(CMe3)2 2 , and Li(Me3C)P? P(SiMe3)(CMe3) 3 with the chlorophosphanes P(SiMe3)(CMe3)Cl, P(CMe3)2Cl, or P(CMe3)Cl2 generate the triphosphanes [(Me3C)(Me3Si)P]2P(SiMe3) 4 , (Me3C)(Me3Si)P? P(SiMe3)? P(CMe3)2 6 , [(Me3C)2P]2P(SiMe3) 7 , and (Me3C)(Me3Si)P? P(SiMe3)? P(CMe3)Cl 8 . The triphosphane (Me3C)2P? P(SiMe3)? P(SiMe3)2 5 is not obtainable as easily. The access to 5 starts by reacting PCl3 with P(SiMe3)(CMe3)2, forming (Me3C)2 P? PCl2, which then with LiP(SiMe3)2 gives (Me3C)2 P? P(Cl)? P(SiMe3)2 11 . Treating 11 with LiCMe3 generates (Me3C)2P? P(H)? P(SiMe3)2 16 , which can be lithiated by LiBu to give (Me3C)2P? P(Li)? P(SiMe3)2 13 and after reacting with Me3SiCl, finally yields 5 . 8 is stable at ?70°C and undergoes cyclization to P3(SiMe3)(CMe3)2 in the course of warming to ambient temperature, while Me3SiCl is split off. 7 , reacting with MeOH, forms [(Me3C)2P]2PH. (Me3C)2P? P(Li)? P(SiMe3)2 18 , which can be obtained by the reaction of 5 with LiBu, decomposes forming (Me3C)2P? P(Li)(SiMe3), P(SiMe3)3, and LiP(SiMe3)2, in contrast to either (Me3C)2P? P(Li)? P(SiMe3)(CMe3) 19 or [(Me3C)2P]2PLi, which are stable in ether solutions. The Li phosphides 1 , 2 , and 3 with BrH2C? CH2Br form the n-tetraphosphanes (Me3C)(Me3Si)P? [P(SiMe3)]2? P(SiMe3)(CMe3) 23 , (Me3C)2P? [P(SiMe3)]2? P(CMe3)2 24 , and (Me3C)(Me3Si)P? [P(CMe3)]2? P(SiMe3)(CMe3) 25 , respectively. Li(Me3Si)P? P(SiMe3)2, likewise, generates (Me3Si)2P? [P(SiMe3)]2? P(SiMe3)2 26 . Just as the n-triphosphanes 4 , 5 , 6 , and 7 , the n-tetraphosphanes 23 , 24 , and 25 can be isolated as crystalline compounds. 23 , treated with LiBu, does nor form any stable n-tetraphosphides, whereas 24 yields (Me3C)2P? P(Li)? P(SiMe3)? P(CMe3)2, that is stable in ethers. With MeOH, 24 , forms crystals of (Me3C)2P? P(H)? P(SiMe3)? P(CMe3)2. 相似文献