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991.
β‐Functionalization of Carboxylic Anhydrides with β‐Alkyl Substituents through Carbene Organocatalysis
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Zhichao Jin Shaojin Chen Yuhuang Wang Pengcheng Zheng Prof. Dr. Song Yang Prof. Dr. Yonggui Robin Chi 《Angewandte Chemie (International ed. in English)》2014,53(49):13506-13509
The first NHC‐catalyzed functionalization of carboxylic anhydrides is described. In this reaction, the β carbon behaves as a nucleophilic carbon and undergoes asymmetric reactions with electrophiles. Anhydrides with challenging β‐alkyl substituents work effectively. 相似文献
992.
Highly Stable Water‐Soluble Platinum Nanoparticles Stabilized by Hydrophilic N‐Heterocyclic Carbenes
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Edwin A. Baquero Dr. Simon Tricard Dr. Juan Carlos Flores Prof. Dr. Ernesto de Jesús Prof. Dr. Bruno Chaudret 《Angewandte Chemie (International ed. in English)》2014,53(48):13220-13224
Controlling the synthesis of stable metal nanoparticles in water is a current challenge in nanochemistry. The strategy presented herein uses sulfonated N‐heterocyclic carbene (NHC) ligands to stabilize platinum nanoparticles (PtNPs) in water, under air, for an indefinite time period. The particles were prepared by thermal decomposition of a preformed molecular Pt complex containing the NHC ligand and were then purified by dialysis and characterized by TEM, high‐resolution TEM, and spectroscopic techniques. Solid‐state NMR studies showed coordination of the carbene ligands to the nanoparticle surface and allowed the determination of a 13C–195Pt coupling constant for the first time in a nanosystem (940 Hz). Additionally, in one case a novel structure was formed in which platinum(II) NHC complexes form a second coordination sphere around the nanoparticle. 相似文献
993.
N‐Alkylacylamides in Thin Films Display Infrared Spectra of 310‐, α‐, and π‐Helices with Visible Static and Dynamic Growth Phases
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A peptide model is a physical system containing a CONH group, the simplest being HCONHCH3, N‐methylformamide (NMF). We have discovered that NMF and N‐methylacetamide (NMA), which form hydrogen‐bonded oligomers in thin films on a planar AgX fiber, display infrared (IR) spectra with peaks like those of polypeptide helices. Structures can be assigned by their amide I maxima near 1672 (310), 1655 (310), 1653 (α), 1655 (π), and 1635 cm?1 (π), which are the first IR data for the π‐helix. Sharp peaks are an outcome of immobilization of polar species on the polar surface of silver halides. We report the first use of expanded thin‐film IR spectroscopy, in which plots of every spectrum over the amide I–II range show pauses or slow stages in the increase or decrease of absorption. These are identified as static phases followed by dynamic phases, with the incremental gain or loss of a helix turn. A general theory can be stated for such processes. Density functional calculations show that the NMA α‐helix pentamer (crystal structure geometry) is transformed into a π‐helix‐like form. For the first time, an entire sequence (310‐helix, α‐helix, π‐helix, quasiplanar species) of spectra has been recorded for NMA. 相似文献
994.
研究了以离子交换法制备的Fe/ZSM-5上聚合态的Fe氧化物(FeOx)在催化N2O直接分解中的作用.Fe/ZSM-5催化剂利用600–900 ℃的高纯Ar处理,使催化剂中的FeOx发生聚合.利用一系列的表征手段(XRD,BET,DRIFTS,UV/vis-DRS,XAFS,N2O脉冲和O2-TPD)对催化剂进行了表征.结果发现,分子筛骨架外的FeOx在Fe/ZSM-5催化N2O分解中起重要作用;通过研究高温处理的Fe/ZSM-5催化剂中不同FeOx的比例与催化剂活性的关系,得到多核的FeOx是催化N2O分解的主要活性物种;并且,无定形态的FeOx中键长较长的Fe–O键((Fe–O)2)是参与反应的重要物种. 相似文献
995.
Dr. Shaoguang Zhang Dr. Peng Cui Tianchang Liu Qiuran Wang Thomas J. Longo Laura M. Thierer Dr. Brian C. Manor Dr. Michael R. Gau Dr. Patrick J. Carroll Prof. Dr. Georgia C. Papaefthymiou Prof. Dr. Neil C. Tomson 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(35):15327-15331
Despite their connection to ammonia synthesis, little is known about the ability of iron-bound, bridging nitrides to form N−H bonds. Herein we report a linear diiron bridging nitride complex supported by a redox-active macrocycle. The unique ability of the ligand scaffold to adapt to the geometric preference of the bridging species was found to facilitate the formation of N−H bonds via proton-coupled electron transfer to generate a μ-amide product. The structurally analogous μ-silyl- and μ-borylamide complexes were shown to form from the net insertion of the nitride into the E−H bonds (E=B, Si). Protonation of the parent bridging amide produced ammonia in high yield, and treatment of the nitride with PhSH was found to liberate NH3 in high yield through a reaction that engages the redox-activity of the ligand during PCET. 相似文献
996.
Mei-Ling Tan Dr. Qing-Hui Guo Dr. Xue-Yuan Wang Tan-Hao Shi Dr. Qian Zhang Sheng-Kai Hou Prof. Dr. Shuo Tong Prof. Dr. Jingsong You Prof. Dr. Mei-Xiang Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23857-23866
Despite the aesthetically appealing structures and tantalizing physical and chemical properties, zigzag hydrocarbon belts and their heteroatom-embedded analogues remain challenging synthetic targets. We report herein the synthesis of diverse O/N-doped zigzag hydrocarbon belts based on selective bridging of the fjords of resorcin[4]arene derivatives through intramolecular SNAr and palladium-catalyzed intermolecular C−N bond formation reactions. Preorganized conformations of mono-macrocyclic, half-belt and quasi-belt compounds were revealed to facilitate cyclization reactions to construct heteroatom-linked octahydrobelt[8]arenes. The acquired products had strained square-prism-shaped belt structures in which all six-membered heterocyclic rings adopted an unusual boat conformation with equatorially configured alkyl groups. The unprecedented heteroatom-bearing belts also exhibited different photophysical and redox properties to those of octahydrobelt[8]arene analogues. 相似文献
997.
998.
Yonggui Liu Dr. Guoyong Luo Dr. Xing Yang Shichun Jiang Prof. Dr. Wei Xue Prof. Dr. Yonggui Robin Chi Prof. Dr. Zhichao Jin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(1):450-456
The aromatic nitrogen atoms of heteroarylaldehydes are activated by carbene catalysts to react with ketone electrophiles. Multi-functionalized cyclic N,O-acetal products are afforded in good to excellent yields and optical purities. Our reaction involves the formation of an unprecedented aza-fulvene-type acylazolium intermediate. A broad range of N-heteroaromatic aldehydes and electron-deficient ketone substrates works effectively in this transformation. Several of the chiral N,O-acetal products afforded through this protocol exhibit excellent antibacterial activities against Ralstonia solanacearum (Rs) and are valuable in the development of novel agrichemicals for plant protection. 相似文献
999.
Mahsa Armaghan Ezzat Najafi Tim-Oliver Knedel Walter Frank Christoph Janiak 《无机化学与普通化学杂志》2020,646(22):1861-1868
Three d10-transition-metal coordination compounds [Cd(tfpb)2(4-bpmh)]n ( 1 ), [Cd(9-aca)(NO3)(OHCH3)(4-bpmh)]n ( 2 ) and [Zn2(dpp)4(4-bpmh)] ( 3 ) with the bridging ligand 4-bpmh were synthesized [4-bpmh = 1,2-bis(pyridin-4-ylmethylene)hydrazine, tfpb = 4,4,4-trifluoro-1-phenylbutane-1,3-dionate, 9-aca = anthracene-9-carboxylate, dpp = 1,3-diphenylpropane-1,3-dionate]. Compounds 1 – 3 were characterized by FT-IR spectroscopy, elemental analysis, and structurally authenticated by X-ray crystallography. Compounds 1 – 3 are constructed by an O,O'-donor ligand including chelating β-diketonates (tfpb, dpp) in 1 and 3 and a carboxylate ligand (9-aca) in 2 in combination with a linear neutral bidentate and bridging N-ligand (4-bpmh). The assembly and action of the bridging 4-bpmh ligand leads to one-dimensional coordination polymers in 1 , 2 and to a dinuclear coordination complex in 3 . The structures and the solid-state supramolecular interactions for studying the crystal packing fashions of 1 – 3 were analyzed. The supramolecular interactions including hydrogen bonding, C–H ··· π, π ··· π, and C–F ··· π in 1 , 2 , and 3 were founded. 相似文献
1000.
作为一种新型非金属材料,石墨相氮化碳以其独特的优点,如简单的制备方法、优良的化学及热稳定性、良好的生物兼容性和无毒性等,受到越来越多的关注。石墨相氮化碳及其复合材料目前已被广泛应用于电催化、光催化、生物成像等领域。由于具有大的比表面积,同时又是富电子的疏水材料,石墨相氮化碳相关材料被认为是一种理想的样品前处理吸附剂。该文探讨了近年来石墨相氮化碳及其复合材料作为固相萃取、分散固相萃取、磁性固相萃取、固相微萃取吸附剂在样品前处理中的应用,并对未来的发展趋势和应用前景进行了展望,以期为相关领域的研究提供帮助。 相似文献