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1.
Thermal Cyclization of Copper Carbenoid of α‐Dizao α‐Phosphorylacetate: Unexpected and Novel Access to Oxaphosphirane 下载免费PDF全文
Under the catalysis of Cu(OTf)2 in refluxing CH2Cl2, ethyl α‐dizao α‐(diethylphosphoryl)acetate was shown to undergo a new cyclization reaction to afford a pentacovalent oxaphosphirane product. The reaction is proposed to occur through the addition of the P=O double bond to the copper carbenoid, followed by the hydrolysis of the ylide intermediate. Our finding represents the first example on producing oxaphosphiranes from dizao phosphoryl compounds. On the other hand, the corresponding rhodium carbenoid displayed the different reactivity under the same thermal conditions, to produce the β‐propiolactone through the well‐recognized C‐H insertion pathway. 相似文献
2.
Po‐Yeng Feng Yi‐Hung Liu Prof. Tien‐Sung Lin Prof. Shie‐Ming Peng Prof. Ching‐Wen Chiu 《Angewandte Chemie (International ed. in English)》2014,53(24):6237-6240
Chemical reduction of a hydroxyphenyl‐substituted borane triggers a sequential electron‐ and intramolecular hydrogen‐atom‐transfer process to afford a hydridoborate phenoxide dianion. On the other hand, hydrogen‐atom abstraction of the borane leads to the isolation of a neutral borylated phenoxyl radical, which can be transformed to the corresponding benzoquinone borataalkene derivative by reduction with cobaltocene. 相似文献
3.
IR,Raman, and Surface‐enhanced Raman Spectroscopic Study on Triruthenium Dipyridylamide Diruthenium Nickel Dipyridylamide Family: Metal‐metal Bonding and Structures 下载免费PDF全文
Yu‐Chun Chiu Kuan‐Yi Ho a I‐Chia Chen Shao‐An Hua Ming‐Chuan Cheng Shie‐Ming Peng 《中国化学会会志》2014,61(12):1289-1296
We report the infrared, Raman, and surface‐enhanced Raman scattering (SERS) spectra of triruthenium dipyridylamido complexes and of diruthenium mixed nickel metal‐string complexes. From the results of analysis on the vibrational modes, we assigned their vibrational frequencies and structures. The infrared band at 323–326 cm?1 is assigned to the Ru3 asymmetric stretching mode for [Ru3(dpa)4Cl2]0–2+. In these complexes we observed no Raman band corresponding to the Ru3 symmetric stretching mode although this mode is expected to have substantial Raman intensity. There is no frequency shift in the Ru3 asymmetric stretching modes for the complexes with varied oxidational states. No splitting in Raman spectra for the pyridyl breathing line indicates similar bonding environment for both pyridyls in dpa– , thus a delocalized structure in the [Ru3]6–8+ unit is proposed. For Ru3(dpa)4(CN)2 complex series, we assign the infrared band at 302 cm?1 to the Ru3 asymmetric stretching mode and the weak Raman line at 285 cm?1 to the Ru3 symmetric stretching. Coordination to the strong axial ligand CN– weakens the Ru‐Ru bonding. For the diruthenium nickel complex [Ru2Ni(dpa)4Cl2]0–1+, the diruthenium stretching mode νRu‐Ru is assigned to the intense band at 327 and 333 cm?1 in the Raman spectra for the neutral and oxidized forms, respectively. This implies a strong Ru‐Ru metal‐metal bonding. 相似文献
4.
Liang‐Yun Wang Jia‐Ling Ko Prof. Chien‐Chen Lai Yi‐Hung Liu Prof. Shie‐Ming Peng Prof. Sheng‐Hsien Chiu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(27):8850-8860
Herein, we report a “threading followed by shrinking” approach for the synthesis of rotaxanes by using an “oxygen‐deficient” macrocycle that contained two arylmethyl sulfone units and the dumbbell‐shaped salt bis(3,5‐dimethylbenzyl)ammonium tetrakis(3,5‐trifluoromethylphenyl)borate as the host and guest components, respectively. The extrusion of SO2 from both of the arylmethyl sulfone units of the macrocyclic component in the corresponding [2]pseudorotaxane resulted in a [2]rotaxane that was sufficiently stable to maintain its molecular integrity in CD3SOCD3 at 393 K for at least 5 h. 相似文献
5.
6.
In this paper, we establish existence theorems of quasivariational inclusion problems; from them, we establish existence theorems
of mathematical programs with quasivariational inclusion constraint, bilevel problems, mathematical programs with equilibrium
constraint and semi-infinite problems.
This research was supported by the National Science Council of the Republic of China. The authors express their gradtitude
to the referees for valuable suggestions. 相似文献
7.
Chien‐Kuo Hsieh Feng‐Chun Lo Gene‐Hsiang Lee Shie‐Ming Peng Wen‐Feng Liaw 《中国化学会会志》2000,47(1):103-107
Complex fac‐[Fe(CO)3(TePh)3]? was employed as a “metallo chelating” ligand to synthesize the neutral (CO)3Mn(μ‐TePh)3Fe(CO)3 obtained in a one‐step synthesis by treating fac‐[Fe(CO)3(TePh)3]? with fac‐[Mn‐(CO)3(CH3CN)3]+. It seems reasonable to conclude that the d6 Fe(II) [(CO)3Fe(TePh)3]? fragment is isolobal with the d6 Mn(I) [(CO)3Mn(TePh)3]2? fragment in complex (CO)3Mn(μ‐TePh)3Fe(CO)3. Addition of fac‐[Fe(CO)3(TePh)3]? to the CpNi(I)(PPh3) in THF resulted in formation of the neutral CpNi(TePh)(PPh3) also obtained from reaction of CpNi(I)(PPh3) and [Na][TePh] in MeOH. This investigation shows that fac‐[Fe(CO)3(TePh)3]? serves as a tridentate metallo ligand and tellurolate ligand‐transfer reagent. The study also indicated that the fac‐[Fe(CO)3(SePh)3]? may serve as a better tridentate metallo ligand and chalcogenolate ligand‐transfer reagent than fac‐[Fe(CO)3(TePh)3]? in the syntheses of heterometallic chalcogenolate complexes. 相似文献
8.
A novel conductive biocomposite film (MWCNTs–DNA–cyt c) which contains multi-walled carbon nanotubes (MWCNTs) along with the incorporation of DNA and cytochrome c (cyt c) has been synthesized on glassy carbon electrode (GCE), gold (Au), indium tin oxide (ITO) and screen printed carbon electrode (SPCE) by potentiostatic methods. The presence of both MWCNTs and DNA in the biocomposite film enhances the surface coverage concentration (Γ), increases the electron transfer rate constant (Ks) up to 21% and decreases the degradation of cyt c during the cycling. The biocomposite film also exhibits a promising enhanced electrocatalytic activity towards the reduction of halogen oxyanions and oxidation of biochemical compounds such as ascorbic acid and l-cysteine. The cyclic voltammetry has been used for the measurement of electroanalytical properties of analytes by means of biocomposite film modified GCEs. The sensitivity of MWCNTs–DNA–cyt c modified GCE possess higher values than the values obtained for DNA–cyt c film modified GCE. Further, the reduction potentials of halogen oxyanions Epc, clearly shows that the activity of the biocomposite is dependent on the electronegativity of halogen oxyanions. Electrochemical quartz crystal microbalance studies revealed the enhancements in the functional properties of MWCNTs, DNA and cyt c. We have studied the surface morphology of the biocomposite films using scanning electron microscopy and atomic force microscopy, which revealed that DNA and cyt c have been incorporated on MWCNTs. Finally, the flow injection analysis has been used for the amperometric detection of analytes at MWCNTs–DNA–cyt c film modified SPCE. 相似文献
9.
Jie‐Ren Shie 《先进技术聚合物》2008,19(1):73-83
This study analyzed contour distortions, wear and tensile properties of polypropylene (PP) components applied in the interior coffer of automobiles. A hybrid method integrating a trained generalized regression neural network (GRNN) and a sequential quadratic programming (SQP) method is proposed to determine an optimal parameter setting of the injection‐molding process. The specimens were prepared under different injection‐molding conditions by changing melting temperatures, injection speeds, and injection pressures. Average contour distortions at six critical locations, wear and tensile properties were selected as the quality targets. Sixteen experimental runs, based on a Taguchi orthogonal array table, were utilized to train the GRNN and then the SQP method was applied to search for an optimal setting. The trained GRNN was capable of predicting average contour distortions, wear and tensile properties at various injection‐molding conditions. In addition, the analysis of variance (ANOVA) was implemented to identify significant factors for the molding process and the proposed algorithm was compared with traditional schemes like the Taguchi method and the design of experiments (DOE) approach. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
10.
The quantum states are presented in these processions of fabricating poly-Si films. Amorphous silicon films prepared by PECVD has been crystallized by conventional furnace annealing (FA) and rapid thermal annealing (RTA), respectively. It is found that the thin films grain size present quantum states with the increasing of the gas flow ratios of SiH4, H2 mixture, substrate temperatures, frequency power, annealing temperature and time. 相似文献