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211.
From a screen of (cyanide)metal complexes, an improved catalyst for the cross silyl benzoin addition was discovered. Several M(CN)(3) complexes (M = Ce, Er, Sm, Y, Yb, La) were evaluated and lanthanum tricyanide was identified as the optimal catalyst. The catalyst, prepared in situ from LaCl(3), effects the selective coupling of aryl and alkyl acylsilanes with aryl, heteroaryl, alpha,beta-unsaturated, and aliphatic aldehydes. The reactions occur at ambient temperature in less than 5 min to provide, depending on the workup, alpha-hydroxy or alpha-silyloxy ketones in 48-93% isolated yield. 相似文献
212.
Jaska CA Temple K Lough AJ Manners I 《Journal of the American Chemical Society》2003,125(31):9424-9434
A mild, catalytic dehydrocoupling route to aminoboranes and borazine derivatives from either primary or secondary amine-borane adducts has been developed using late transition metal complexes as precatalysts. The adduct Me(2)NH.BH(3) thermally eliminates hydrogen at 130 degrees C in the condensed phase to afford [Me(2)N-BH(2)](2) (1). Evidence for an intermolecular process, rather than an intramolecular reaction to form Me(2)N=BH(2) as an intermediate, was forthcoming from "hot tube" experiments where no appreciable dehydrocoupling of gaseous Me(2)NH.BH(3) was detected in the range 150-450 degrees C. The dehydrocoupling of Me(2)NH.BH(3) was found to be catalyzed by 0.5 mol % [Rh(1,5-cod)(mu-Cl)](2) in solution at 25 degrees C to give 1 quantitatively after ca. 8 h. The rate of dehydrocoupling was significantly enhanced if the temperature was raised or if the catalyst loading was increased. The catalytic activity of various other transition metal complexes (Ir, Ru, Pd) for the dehydrocoupling of Me(2)NH.BH(3) was also demonstrated. This new catalytic method was extended to other secondary adducts RR'NH.BH(3) which afforded the dimeric species [(1,4-C(4)H(8))N-BH(2)](2) (2) and [PhCH(2)(Me)N-BH(2)](2) (3) or the monomeric aminoborane (i)Pr(2)N=BH(2) (4) under mild conditions. A new synthetic approach to the linear compounds R(2)NH-BH(2)-NR(2)-BH(3) (5: R = Me; 6: R = 1,4-C(4)H(8)) was developed and subsequent catalytic dehydrocoupling of these species yielded the cyclics 1 and 2. The species 5 and 6 are postulated to be intermediates in the formation of 1 and 2 directly from the catalytic dehydrocoupling of the adducts R(2)NH.BH(3). The catalytic dehydrocoupling of NH(3).BH(3), MeNH(2).BH(3), and PhNH(2).BH(3) at 45 degrees C to give the borazine derivatives [RN-BH](3) (10: R = H; 11: R = Me; 12: R = Ph) was demonstrated. TEM analysis of the contents of the reaction solution for the [Rh(1,5-cod)(mu-Cl)](2) catalyzed dehydrocoupling of Me(2)NH.BH(3) together with Hg poisoning experiments suggested a heterogeneous catalytic process involving Rh(0) colloids. 相似文献
213.
Landi BJ Ruf HJ Evans CM Cress CD Raffaelle RP 《The journal of physical chemistry. B》2005,109(20):9952-9965
A demand currently exists for a method of assessing the purity of single-wall carbon nanotubes (SWNTs), which will allow for meaningful material comparisons. An established metric and protocol will enable accurate and reproducible purity claims to be substantiated. In the present work, the ability to accurately quantify the mass fraction of SWNTs in the carbonaceous portion of a given sample is demonstrated, using optical absorption spectroscopy on both laser and arc discharge-generated SWNT-N,N-dimethylacetamide (DMA) dispersions. Verification of purity assessment protocols is based upon constructed sample sets comprising designed mass fractions of purified SWNTs and representative carbonaceous synthesis byproducts. Application of a previously reported method based on a ratio of the areal absorbance from linear subtractions of the second interband electronic transitions of semiconducting SWNTs ((S)E(22)) has shown a severe overestimation of SWNT purity (average error >24%). Instead, the development of a nonlinear pi-plasmon model, which considers overlap of electronic transitions and peak broadening, has dramatically improved the purity assessment accuracy (average error <7%), derived from a strong correlation to the constructed sample sets. This approach has enabled corroboration of rapid assessment procedures, such as absorbance peak maxima ratio and Beer's law analysis, directed at purification monitoring and synthesis sample screening. Specifically, a simple protocol for purity assessment of laser and arc-discharge SWNTs has been established that can be extended to other synthetic types (i.e. CVD, HiPco, etc.) and diameter distributions. 相似文献
214.
This paper analyzes the effect of mixing on nucleation of protein crystals. The mixing of protein and precipitant was controlled by changing the flow rate in a plug-based microfluidic system. The nucleation rate inversely depended on the flow rate, and flow rate could be used to control nucleation. For example, at higher supersaturations, precipitation happened at low flow rates while large crystals grew at high flow rates. Mixing at low flow velocities in a winding channel induces nucleation more effectively than mixing in straight channels. A qualitative scaling argument that relies on a number of assumptions is presented to understand the experimental results. In addition to helping fundamental understanding, this result may be used to control nucleation, using rapid chaotic mixing to eliminate formation of precipitates at high supersaturation and using slow chaotic mixing to induce nucleation at lower supersaturation. 相似文献
215.
The identification of two natural products, FR-900848 and U-106305, has stimulated interest concerning the relationship between configurational isomerism, conformational isomerism, and biological activity of polycyclopropanes. Efforts to investigate the relationship between configurational and conformational isomerism through molecular modeling suggest that significantly different three-dimensional structures will result from unique primary structures. Any effort to address these issues demands that stereoselective methods for the preparation of polycyclopropanes be developed. We have investigated the application of zinc-carbenoid cyclopropanation in the presence of chiral dioxaboralanes to the preparation of eight stereochemically unique bicyclopropanes. The trans-vinylcyclopropane starting materials demonstrated very little substrate-induced stereoselectivity, while the cis-vinylcyclopropane demonstrates modest to excellent stereocontrol. A model for the substrate-based stereocontrol is proposed. We also used the spectroscopic data gathered in this investigation to probe the substrate-mediated stereocontrol in the rhodium(II)-catalyzed cyclopropanation of vinylcyclopropanes with ethyl diazoacetate. 相似文献
216.
Experimental demonstration of fully coherent quantum feedback 总被引:2,自引:0,他引:2
In the conventional picture of quantum feedback, control sensors make measurements on a quantum system, a classical controller processes the results of the measurements, and semiclassical actuators act back on the system to alter its behavior. We describe and provide an experimental demonstration of an alternative method for quantum feedback control, in which the sensors, controller, and actuators of conventional feedback control are replaced with quantum systems that interact coherently with the system to be controlled. The resulting control system represents a fully coherent quantum feedback loop. 相似文献
217.
Mair RW Tseng CH Wong GP Cory DG Walsworth RL 《Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics》2000,61(3):2741-2748
We demonstrate nuclear magnetic resonance (NMR) imaging of the flow and diffusion of laser-polarized xenon (129Xe) gas undergoing convection above evaporating laser-polarized liquid xenon. The large xenon NMR signal provided by the laser-polarization technique allows more rapid imaging than one can achieve with thermally polarized gas-liquid systems, permitting shorter time-scale events such as rapid gas flow and gas-liquid dynamics to be observed. Two-dimensional velocity-encoded imaging shows convective gas flow above the evaporating liquid xenon, and also permits the measurement of enhanced gas diffusion near regions of large velocity variation. 相似文献
218.
Valente C Baglione S Candito D O'Brien CJ Organ MG 《Chemical communications (Cambridge, England)》2008,(6):735-737
High yielding, room temperature cross couplings of unactivated alkyl bromides and aryl bromides/chlorides with alkyl-9-BBN reagents has been achieved using an NHC-based catalyst (Pd-PEPPSI-IPr) via a general, functional-group tolerant and easily implemented protocol. 相似文献
219.
Dr. Yunling Deng Dr. Sudharsan Dwaraknath Wenhao O. Ouyang Cory J. Matsumoto Stephanie Ouchida Prof. Dr. Yi Lu 《Angewandte Chemie (International ed. in English)》2023,62(20):e202215719
While native CO2-reducing enzymes display remarkable catalytic efficiency and product selectivity, few artificial biocatalysts have been engineered to allow understanding how the native enzymes work. To address this issue, we report cobalt porphyrin substituted myoglobin (CoMb) as a homogeneous catalyst for photo-driven CO2 to CO conversion in water. The activity and product selectivity were optimized by varying pH and concentrations of the enzyme and the photosensitizer. Up to 2000 TON(CO) was attained at low enzyme concentrations with low product selectivity (15 %), while a product selectivity of 74 % was reached by increasing the enzyme loading but with a compromised TON(CO). The efficiency of CO generation and overall TON(CO) were further improved by introducing positively charged residues (Lys or Arg) near the active stie of CoMb, which demonstrates the value of tuning the enzyme secondary coordination sphere to enhance the CO2-reducing performance of a protein-based photocatalytic system. 相似文献
220.
W E Maas A Bielecki M Ziliox F H Laukien D G Cory 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1999,141(1):29-33
Magnetic field gradients have proven useful in NMR for coherence pathway selection, diffusion studies, and imaging. Recently they have been combined with magic angle spinning to permit high-resolution measurements of semi-solids, where magic angle spinning averages any residual dipolar couplings and local variations in the bulk magnetic susceptibility. Here we show the first examples of coherence pathway selection by gradients in dipolar coupled solids. When the gradient evolution competes with dipolar evolution the experiment design must take into account both the strength of the dipolar couplings and the means to refocus it. Examples of both homonuclear and heteronuclear experiments are shown in which gradients have been used to eliminate the need for phase cycling. 相似文献