Rhenium hydride/boron Lewis acid cocatalysis of alkene hydrogenations: activities comparable to those of precious metal systems

Dibromonitrosyl(dihydrogen)rhenium(I) complexes [ReBr(2)(NO)(PR(3))(2)(η(2)-H(2))] (1; R = iPr, a; Cy, b) and Me(2)NH·BH(3) (DMAB) catalyze at either 90 °C or ambient temperature under 10 bar of H(2) the hydrogenation of various terminal and cyclic alkenes (1-hexene, 1-octene, cyclooctene, styrene, 1,5-cyclooctadiene, 1,7-octadiene, α-methylstyrene). Maximum turnover frequency (TOF) values of 3.6 × 10(4) h(-1) at 90 °C and 1.7 × 10(4) h(-1) at 23 °C were achieved in the hydrogenation of 1-hexene. The extraordinary catalytic performance of the 1/DMAB system is attributed to the formation of five-coordinate rhenium(I) hydride complexes [Re(Br)(H)(NO)(PR(3))(2)] (2; R = iPr, a; Cy, b) and the action of the Lewis acid BH(3) originating from DMAB. The related 2/BH(3)·THF catalytic system also exhibits under the same conditions high activity in the hydrogenation of various alkenes with a maximum turnover number (TON) of 1.2 × 10(4) and a maximum TOF of 4.0 × 10(4) h(-1). For the hydrogenations of 1-hexene with 2a and 2b, the effect of the strength of the boron Lewis acid was studied, the acidity being in the following order: BCl(3) > BH(3) > BEt(3) ≈ BF(3) > B(C(6)F(5))(3) > BPh(3) ? B(OMe)(3). The order in catalytic activity was found to be B(C(6)F(5))(3) > BEt(3) ≈ BH(3)·THF > BPh(3) ? BF(3)·OEt(2) > B(OMe)(3) ? BCl(3). The stability of the catalytic systems was checked via TON vs time plots, which revealed the boron Lewis acids to cause an approximate inverse order with the Lewis acid strength: BPh(3) > BEt(3) ≈ BH(3)·THF > B(C(6)F(5))(3). For the 2a/BPh(3) system a maximum TON of 3.1 × 10(4) and for the 2a/B(C(6)F(5))(3) system a maximum TOF of 5.6 × 10(4) h(-1) were obtained in the hydrogenation of 1-hexene. On the basis of kinetic isotope effect determinations, H(2)/D(2) scrambling, halide exchange experiments, Lewis acid variations, and isomerization of terminal alkenes, an Osborn-type catalytic cycle is proposed with olefin before H(2) addition. The active rhenium(I) monohydride species is assumed to be formed via reversible bromide abstraction with the "cocatalytic" Lewis acid. Homogeneity of the hydrogenations was tested with filtration and mercury poisoning experiments. These "rhenium(I) hydride/boron Lewis acid" systems demonstrate catalytic activities comparable to those of Wilkinson- or Schrock-Osborn-type hydrogenations accomplished with precious metal catalysts.     

堆焊熔敷层表面纳米晶层摩擦磨损性能研究

用预压力滚压技术在堆焊修复层表面制备纳米晶层.利用TEM、SEM分析技术研究表面纳米晶层微观结构,利用CETR-3型多功能摩擦磨损试验机考察在干摩擦条件下堆焊层表面纳米晶层的摩擦磨损性能.结果表明堆焊修复层表面经表面纳米化处理后,表面形成厚度约为10μm(晶粒尺寸小于100 nm)的纳米晶层,最表面层平均晶粒尺寸约为10 nm.纳米压痕试验表明纳米晶层的硬度提高,最表面纳米晶层的硬度约为原始堆焊层硬度的3倍.与原始堆焊试样相比,表面纳米化试样的摩擦系数降低了10%,磨损体积降低了25%~30%左右.表面纳米化样品的磨损机制由原始堆焊层的磨粒磨损和黏着磨损转变为磨粒磨损,分析表明晶粒细化导致的高硬度、低塑性是摩擦磨损性能改善和磨损机制改变的主要原因.     

Spin gap in the zigzag spin-1/2 chain cuprate Sr(0.9)Ca(0.1)CuO(2)

We report a comparative study of (63)Cu nuclear magnetic resonance spin lattice relaxation rates T(1)(-1) on undoped SrCuO(2) and Ca-doped Sr(0.9)Ca(0.1)CuO(2) spin chain compounds. A temperature independent T(1)(-1) is observed for SrCuO(2) as expected for an S=1/2 Heisenberg chain. Surprisingly, we observe an exponential decrease of T(1)(-1) for T<90 K in the Ca-doped sample evidencing the opening of a spin gap. The data analysis within the J(1)-J(2) Heisenberg model employing density-matrix renormalization group calculations suggests an impurity driven small alternation of the J(2)-exchange coupling as a possible cause of the spin gap.     

Search for direct photons from S-Au collisions at 200 GeV/nucleon

The CERES experiment has measured inclusive photon production in S-Au collisions of 200 GeV/nucleon at the CERN SPS. No evidence for direct emission of photons was found. For the kinematic region 2.1<y<2.65 and 0.4 GeV/c<p??<2.0 GeV/c the yield andp??-dependence of the observed photons are well reproduced by hadron decays. Furthermore, their production rate is found to be proportional to the charged particle density. The systematic errors comparing the measured and expected photon yield result in an upper limit of 14% for the emission of direct photons in central S-Au collisions. For a photon source with a yield depending quadratically on the charged particle density the limit can be reduced to 7%.     

Preparation, IR spectroscopy, and time-of-flight mass spectrometry of halogenated and methylated Si(111)

The preparation of chlorine-, bromine-, and iodine-terminated silicon surfaces (Si(111):Cl, Br, and I) using atomically flat Si(111)-(1×1):H is described. The halogenated surfaces were obtained by photochemically induced radical substitution reactions with the corresponding dihalogen in a Schlenk tube by conventional inert gas chemistry. The nucleophilic substitution of the Si-Cl functionality with the Grignard reagent (CH₃MgCl) resulted in the unreconstructed methylated Si(111)-(1×1):CH₃ surface. The halogenated and methylated silicon surfaces were characterized by Fourier transform infrared (FTIR) spectroscopy and laser-induced desorption of monolayers (LIDOM). Calibration of the desorption temperature via analysis of time-of-flight (TOF) distributions as a function of laser fluence allowed the determination of the originally emitted neutral fragments by TOF mass spectrometry using electron-impact ionization. The halogens were desorbed atomically and as SiX _n (X = Cl, Br) clusters. The methyl groups mainly desorbed as methyl and ethyl fragments and a small amount of ⁺SiCH₃.     

Real-time probing of vectorial properties of ultra-fast photodissociations in liquids

Polarization-resolved femtosecond experiments are shown to yield valuable insight into transition-state dynamics associated with ultra-fast photodissociation reactions of triatomic species in liquid solution. After the fundamental act of bond fission is completed, such experiments reveal rotational dynamics of the fragments, which can be used to extract information regarding fragment rotational excitation in the asymptotic limit of the reaction. Received: 4 October 1999 / Published online: 30 June 2000     

Qualitative and quantitative analysis of voice onset by means of a multidimensional voice analysis system (MVAS) using high-speed imaging

High-speed filming is one of the most informative methods for assessing voice physiology data. Tracing high-speed images of the glottis provides quantitative parameters such as the glottal area and the glottal width function. By way of example, a number of studies are discussed which extract quantitative data from high-speed images showing voice onsets. Furthermore, a new computer system (MVAS; multi-dimensional voice analysis system) is presented that synchronously displays a laryngoscopic high-speed film, the electroglottographical signal, and several acoustic analyses of the recorded voice sample. The automatic measurement of glottal width and glottal area from the laryngoscopic images is also provided. Looking at former studies and our analyses of voice onsets reveals a tremendous intersubject and even intrasubject variability (different prephonatory closure, different time span until full amplitude is reached, different open quotient).     

Identification and separation of saxitoxins using hydrophilic interaction liquid chromatography coupled to traveling wave ion mobility‐mass spectrometry

The aim of this work was to develop a reliable and efficient analytical method to characterise and differentiate saxitoxin analogues (STX), including sulphated (gonyautoxins, GTX) and non‐sulphated analogues. For this purpose, hydrophilic interaction liquid chromatography (HILIC) was used to separate sulphated analogues. We also resorted to ion mobility spectrometry to differentiate the STX analogues because this technique adds a new dimension of separation based on ion gas phase conformation. Positive and negative ionisation modes were used for gonyautoxins while positive ionisation mode was used for non‐sulphated analogues. Subsequently, the coupling of these three complementary techniques, HILIC‐IM‐MS, permitted the separation and identification of STX analogues; isomer differentiation was achieved in HILIC dimension while non‐sulphated analogues were separated in the IM‐MS dimension. Additional structural characteristics concerning the conformation of STXs could be obtained using IM‐MS measurements. Thus, the collision cross sections (CCS) of STXs are reported for the first time in the positive ionisation mode. These experimental CCSs correlated well with the calculated CCS values using the trajectory method. Copyright © 2015 John Wiley & Sons, Ltd.