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1.
Iwao Omae 《应用有机金属化学》2009,23(3):91-107
Group 9 metal compounds in organic synthesis have two characteristic reactions. The first occurs because the group 9 metals have a high affinity to carbon–carbon or carbon–nitrogen π‐bonds. The first type of characteristic reactions in these group 9 metal compounds includes Pauson–Khand reactions, the Pauson–Khand‐type reactions ([2 + 2 + 1] cyclization), the other cyclizations and coupling reactions. The second occurs because the group 9 metals have a high affinity to carbonyl groups. The second type of characteristic reactions includes carbonylations such as hydroformylations, the carbonylations of methanol, amidocarbonylations and other carbonylations. The first characteristic reactions are applied for the synthesis of fine chemicals such as pharmaceuticals and agrochemicals. However, the second characteristic reactions are utilized not only for fine chemicals but also for important bulk commodity chemicals such as aldehydes, carboxylic acids and alcohols. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
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Eiji Ihara Takao Wake Naoki Mokume Tomomichi Itoh Kenzo Inoue 《Journal of polymer science. Part A, Polymer chemistry》2006,44(19):5661-5671
α,α‐Dibromotoluene 1 was found to be polymerized by the reaction with excess Mg to give poly(phenylmethylene)s 2 , whose main chains were partially dehydrogenated to carbon–carbon double bonds (C?C). The C?Cs in 2 can be brominated by treatment with Br2. The polymerization mechanism was presumed to include the formation of Grignard reagents of various species with benzylic C? Br bonds and the nucleophilic attacks of the Grignard reagents to various compounds with benzylic C? Br bonds. Copolymerization of 1 with dichlorodimethylsilane successfully proceeded. Mg/Cu‐mediated copolycondensation of 1 with 1,6‐dibromohexane proceeded to give polymers that have similar compositions to those of random copolymers of ethylene and styrene. © 2006Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5661–5671, 2006 相似文献
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J Yamaguchi AD Yamaguchi K Itami 《Angewandte Chemie (International ed. in English)》2012,51(36):8960-9009
The direct functionalization of C? H bonds in organic compounds has recently emerged as a powerful and ideal method for the formation of carbon–carbon and carbon–heteroatom bonds. This Review provides an overview of C? H bond functionalization strategies for the rapid synthesis of biologically active compounds such as natural products and pharmaceutical targets. 相似文献
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有机金属化合物是指分子中至少含有一个金属-碳键(M-C键)的化合物,包括含M-C σ-键、M-Cnπ-键、ηn-M-Cn大π-键的化合物.双核金属-金属碳键的有机化合物的光化学反应包括光诱导金属-金属键的断裂、配体的离解与取代、光化学插入反应、光诱导异构化反应、歧化反应等. 相似文献
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Density functional calculations on several classes of organolithium compounds are described. The compounds studied include lithium bonds to carbon, oxygen, and nitrogen and are representative of most types of organolithium compounds that have appeared in the recent literature. The computational results are compared to those using MNDO, which has been shown to have some serious deficiencies in compounds involving carbon–lithium bonds, and to PM3 results, which offer some improvement over MNDO for many organolithium compounds. Most of the density functional calculations with a large basis set are in good agreement with available ab initio and experimental data. Calculated carbon–lithium bond lengths were slightly shorter than those calculated by other ab initio methods and were substantially longer than those calculated by MNDO, which is known to underestimate carbon–lithium bond lengths severely. Dimerization energies of methyllithium, calculated by DMol, were also in good agreement with those of other ab initio calculations. Lithium–nitrogen bonds in lithium amides were calculated to be slightly shorter by DMol than by MNDO, although the two methods were in qualitative agreement for this type of compound. © 1995 by John Wiley & Sons, Inc. 相似文献
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Synthesis,Structural Characterization and Preliminary Biological Studies of Several Heterocyclic Transition Metal Carbonyl Complexes 下载免费PDF全文
Shanfang Hu Xianwei Cui Weimin He Xiangyi Chen Zikuan Gu Jingzhe Zhao Guang Zeng Zhan Shi Lei Zhu Hemin Nie 《无机化学与普通化学杂志》2015,641(14):2452-2459
The reaction of molybdenum, tungsten and manganese carbonyls with several thiazole heterocycle ligands yielded a number of coordinated transition metal complexes 1 – 10 . Of these complexes 1 – 6 are new compounds which have not been reported to date. The structures of new compounds were characterized by FT‐IR and 1H‐NMR spectroscopy as well as single‐crystal X‐ray diffraction analysis. Complexes 1 – 10 are carbon monoxide releasing molecules that show structure‐related anti‐cancer activity. The cytotoxicity of all compounds on Hela cells was evaluated by MTT assay, and the results show that carbon monoxide releasing molecules containing such Schiff base ligands may have biomedical applications for their anti‐tumor effect. 相似文献
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Iwao Omae 《应用有机金属化学》2008,22(3):149-166
Alkynes have two sets of mutually orthogonal π‐bonds that are different from the π‐bonds of alkenes. These π‐bonds are able to bond with transition metal compounds. Alkynes easily bond with the various kinds of compounds having a π‐bond such as carbon monoxide, alkenes, other alkynes and nitriles in the presence of the transition metal compounds. The most representative reaction of alkynes is called the Pauson–Khand reaction. The Pauson–Khand reactions include the cyclization of alkynes with alkenes and carbon monoxide in the presence of cobalt carbonyls. Similar Pauson–Khand reactions also proceed in the presence of other transition metal compounds. These reactions are the first type of characteristic reaction of alkynes. Other various kinds of cyclizations with alkynes also proceed in the presence of the transition metal compounds. These reactions are the second type of characteristic reaction of alkynes. These include cyclooligomerizations and cycloadditions. The cyclooligomerizations include mainly cyclotrimerizations and cyclotetramerizations, and the cycloadditions are [2 + 2], [2 + 2 + 1], [2 + 2 + 2], [3 + 2], [4 + 2], etc., type cycloadditions. Alkynes are fairly reactive because of the high s character of their σ‐bonds. Therefore, simple coupling reactions with alkynes also proceed besides the cyclizations. The coupling reactions are the third type of characteristic reactions of alkynes in the presence of, mainly, the transition metal compounds. These reactions include carbonylations, dioxycarbonylations, Sonogashira reactions, coupling reactions with aldehydes, ketones, alkynes, alkenes and allyl compounds. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
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Xinyu Zhao Dr. Lige Gong Chunxiao Wang Prof. Chunmei Wang Prof. Dr. Kai Yu Prof. Dr. Baibin Zhou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(20):4613-4619
Successful synthesis of three kinds of dynamically stable compounds by a simple grinding method is reported, giving Ag6Mo7O24, Ag-BTC (Ag-MOF, BTC=benzene-1,3,5-tricarboxylic acid), and {Ag6Mo7O24}@Ag-MOF metal–organic frameworks (MOFs). According to the electrochemical dynamic analysis, these materials have pseudocapacitor behavior and high capacitance. The unique nanorod structure of {Ag6Mo7O24}@Ag-MOF provides more active sites, faster ion/electron transfer, and electrolyte diffusion pathways, resulting in excellent specific capacitance (971 F g−1) higher than the other compounds. {Ag6Mo7O24}@Ag-MOF (glassy carbon electrode) also has an excellent rate ability (60.1 %) and long cycle stability (98 % retention after 5000 cycles). In addition, the fully symmetrical button battery (with nickel foam as the current collector) fabricated with {Ag6Mo7O24}@Ag-MOF delivers an energy density of 11.1 Wh kg−1 at 600.1 Wh kg−1 coupled with excellent cycling stability (86.4 %) at 1.2 V. These results demonstrate a new simple grinding method to prepare polyoxometalate-based metal–organic frameworks (POMOFs) for high-performance materials. 相似文献
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K. V. Katok V. A. Tertykh S. Ya. Brichka G. P. Prikhod’ko 《Journal of Thermal Analysis and Calorimetry》2006,86(1):109-114
Pyrolytic decomposition of acetylene over the surface of nickel-, cobalt-
and iron-containing ordered mesoporous MCM-41 silicas has been studied. Catalytically
active matrices have been prepared by chemisorption of volatile metal acetylacetonate
complexes on the silica surface. Reduction of the supported metal-containing
compounds was carried out in hydrogen or acetylene atmosphere. Acetylene is
used not only as a source of carbon in synthesis of the nanostructures but
also as a reagent capable of reducing metal ions in the surface chemical compounds.
Formation of carbon nanotubes and nanofibers is shown to depend on the pyrolysis
conditions. 相似文献
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《Journal of separation science》2017,40(20):3969-3975
Metal–organic frameworks‐5 (MOF‐5) was explored as a template to prepare porous carbon due to its high surface area, large pore volume, and permanent nanoscale porosity. Magnetic porous carbon, Co@MOF‐5‐C, was fabricated by the one‐step direct carbonization of Co‐doped MOF‐5. After carbonization, the magnetic cobalt nanoparticles are well dispersed in the porous carbon matrix, and Co@MOF‐5‐C displays strong magnetism (with the saturation magnetization intensity of 70.17emu/g), high‐specific surface area, and large pore volume. To evaluate its extraction performance, the Co@MOF‐5‐C was applied as an adsorbent for the magnetic solid‐phase extraction of endocrine disrupting chemicals, followed by their analysis with high‐performance liquid chromatography. The developed method exhibits a good linear response in the range of 0.5–100 ng/mL for pond water and 1.0–100 ng/mL for juice samples. The limits of detection (S/N = 3) for the analytes were in the range of 0.1–0.2 ng/mL. 相似文献
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Dr. Hanyuan Li Biao Ma Qi-Sheng Liu Mei-Ling Wang Zhen-Yu Wang Hui Xu Ling-Jun Li Xing Wang Prof. Dr. Hui-Xiong Dai 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(34):14494-14499
The coupling of aromatic electrophiles (aryl halides, aryl ethers, aryl acids, aryl nitriles etc.) with nucleophiles is a core methodology for the synthesis of aryl compounds. Transformations of aryl ketones in an analogous manner via carbon–carbon bond activation could greatly expand the toolbox for the synthesis of aryl compounds due to the abundance of aryl ketones. An exploratory study of this approach is typically based on carbon–carbon cleavage triggered by ring-strain release and chelation assistance, and the products are also limited to a specific structural motif. Here we report a ligand-promoted β-carbon elimination strategy to activate the carbon–carbon bonds, which results in a range of transformations of aryl ketones, leading to useful aryl borates, and also to biaryls, aryl nitriles, and aryl alkenes. The use of a pyridine-oxazoline ligand is crucial for this catalytic transformation. A gram-scale borylation reaction of an aryl ketone via a simple one-pot operation is reported. The potential utility of this strategy is also demonstrated by the late-stage diversification of drug molecules probenecid, adapalene, and desoxyestrone, the fragrance tonalid as well as the natural product apocynin. 相似文献
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S. Legand C. Bouyer V. Dauvois F. Casanova D. Lebeau C. Lamouroux 《Journal of Radioanalytical and Nuclear Chemistry》2014,302(1):27-39
The direct dissolution of UC, a potential fuel for generation-IV nuclear reactors, in nitric acid can produce organic complexants that may interfere with the consumed fuel reprocessing based on liquid–liquid extraction. This study shows the presence of 17 % of carboxylic and polycarboxylic acids (e.g. benzenepentacarboxylic acid). 25 % of the carbon mass balance seemed to correspond to unfunctionalized polyaromatic compounds with more than 3–4 aromatic rings. Under an active oxidation process, these compounds become smaller and very functionalized polyaromatic compounds. Structures have been proposed for 8 % of the carbon mass balance. 相似文献
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Hanyuan Li Biao Ma Qi‐Sheng Liu Mei‐Ling Wang Zhen‐Yu Wang Hui Xu Ling‐Jun Li Xing Wang Hui‐Xiong Dai 《Angewandte Chemie (International ed. in English)》2020,59(34):14388-14393
The coupling of aromatic electrophiles (aryl halides, aryl ethers, aryl acids, aryl nitriles etc.) with nucleophiles is a core methodology for the synthesis of aryl compounds. Transformations of aryl ketones in an analogous manner via carbon–carbon bond activation could greatly expand the toolbox for the synthesis of aryl compounds due to the abundance of aryl ketones. An exploratory study of this approach is typically based on carbon–carbon cleavage triggered by ring‐strain release and chelation assistance, and the products are also limited to a specific structural motif. Here we report a ligand‐promoted β‐carbon elimination strategy to activate the carbon–carbon bonds, which results in a range of transformations of aryl ketones, leading to useful aryl borates, and also to biaryls, aryl nitriles, and aryl alkenes. The use of a pyridine‐oxazoline ligand is crucial for this catalytic transformation. A gram‐scale borylation reaction of an aryl ketone via a simple one‐pot operation is reported. The potential utility of this strategy is also demonstrated by the late‐stage diversification of drug molecules probenecid, adapalene, and desoxyestrone, the fragrance tonalid as well as the natural product apocynin. 相似文献
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V. D. Voronchikhin M. A. Khudolei K. A. Dubkov D. P. Ivanov S. V. Semikolenov 《Russian Journal of Applied Chemistry》2017,90(4):582-587
Samples of carbon–oligomer filler prepared by ketonization of tire rubber crumb with dinitrogen monoxide were characterized. The effect of the oligomeric component of the filler on the kinetic parameters of cross-linking in model compounds was determined. A study of the main rheological and physicomechanical properties of elastomer compounds based on butadiene–α-methylstyrene rubber containing carbon–oligomer filler demonstrated the possibility of using it as a component of polyfunctional action. 相似文献
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Jacqueline Pollini Dr. Wolf M. Pankau Prof. Lukas J. Gooßen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(31):7416-7425
Isomerizing olefin metathesis is currently undergoing a transformation from laboratory curiosity to powerful synthetic concept at the heart of orthogonal tandem catalysis. In this process, an isomerization catalyst continuously moves double bonds along carbon chains, while a metathesis catalyst scrambles the residues at the C−C double bonds. This cooperative action of two catalysts can be used to access single, defined products from a complex mixture of compounds. Alternatively, it enables the transformation of uniform starting materials into complex product blends with defined, tunable properties. This concept article highlights recent developments and potential applications of this fascinating reaction concept. 相似文献
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Valérie Wathelet Julien Preat Michaël Bouhy Michèle Fontaine Eric A. Perpète Jean-Marie André Denis Jacquemin 《International journal of quantum chemistry》2006,106(8):1853-1859
Using the parameter‐free PBE0 hybrid functional, we compute the UV/Vis spectra of a series of solvated compounds presenting a carbonyl chromophoric unit linked to a carbon–carbon double bond. It turns out that PBE0 is extremely efficient for accurately reproducing experimental values, with a mean unsigned error of 7 nm for an extended set of compounds, although no fitting or statistical treatments are performed. PBE0 has a predictive efficiency comparable to the well‐known Woodward–Fieser empirical formula, and can therefore be used to extend these rules without requiring additional experimental results. Consequently, the UV/Vis spectra of several compounds that have not yet been synthesized are predicted. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 相似文献