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41.
Dr. Jelena D. Nikolić Dr. Sebastian Wouters Dr. Julia Romanova Dr. Akihiro Shimizu Prof. Dr. Benoît Champagne Prof. Dr. Thomas Junkers Prof. Dr. Dirk Vanderzande Prof. Dr. Dimitri Van Neck Prof. Dr. Michel Waroquier Prof. Dr. Veronique Van Speybroeck Prof. Dr. Saron Catak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(52):19176-19185
Despite various studies on the polymerization of poly(p‐phenylene vinylene) (PPV) through different precursor routes, detailed mechanistic knowledge on the individual reaction steps and intermediates is still incomplete. The present study aims to gain more insight into the radical polymerization of PPV through the Gilch route. The initial steps of the polymerization involve the formation of a p‐quinodimethane intermediate, which spontaneously self‐initiates through a dimerization process leading to the formation of diradical species; chain propagation ensues on both sides of the diradical or chain termination occurs by the formation of side products, such as [2.2]paracyclophanes. Furthermore, different p‐quinodimethane systems were assessed with respect to the size of their aromatic core as well as the presence of heteroatoms in/on the conjugated system. The nature of the aromatic core and the specific substituents alter the electronic structure of the p‐quinodimethane monomers, affecting the mechanism of polymerization. The diradical character of the monomers has been investigated with several advanced methodologies, such as spin‐projected UHF, CASSCF, CASPT2, and DMRG calculations. It was shown that larger aromatic cores led to a higher diradical character in the monomers, which in turn is proposed to cause rapid initiation. 相似文献
42.
Coating Platinum Nanoparticles with Methyl Radicals: Effects on Properties and Catalytic Implications 下载免费PDF全文
Dr. Ronen Bar‐Ziv Dr. Israel Zilbermann Dr. Michael Shandalov Prof. Dr. Vladimir Shevchenko Prof. Dr. Dan Meyerstein 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(52):19000-19009
It was recently reported that the reaction of methyl radicals with Pt0 nanoparticles (NPs), prepared by the reduction of Pt(SO4)2 with NaBH4, is fast and yields as the major product stable (Pt0‐NPs)?(CH3)n and as side products, in low yields, C2H6, C2H4, and some oligomers. We decided to study the effect of this coating on the properties of the Pt0‐NPs. The results show that the coating can cover up to 75 % of the surface Pt0 atoms. The rate constant of the reaction, k( . CH3+Pt0‐NPs), decreases with the increase in the surface coverage, leading to competing reaction paths in the solution, which gradually become dominant, affecting the composition of the products. The methyl coating also affects the zeta potential, the UV spectra, and the electrocatalytic reduction of water in the presence of the NPs. Thus, the results suggest that binding alkyl radicals to Pt0 surfaces might poison the NPs catalytic activity. When the Pt0‐NPs are prepared by the reduction of a different precursor salt, PtCl62?, nearly no C2H4 and oligomers are formed and the methyl coating covers a larger percentage of the surface Pt0 atoms. The difference is attributed to the morphology of the Pt0‐NPs: those prepared from Pt(SO4)2 are twinned nanocrystals, whereas those prepared from PtCl62? consist mostly of single crystals. Thus, the results indicate that the side products, or most of them at least, are formed on the twinned Pt0 nanocrystal edges created between (111) facets. In addition, the results show that Pt0‐NPs react very differently compared with other noble metals, for example, Au0 and Ag0; this difference is attributed in part to the difference in the bond strength, (M0‐NP)?CH3, and should be considered in heterogeneous catalytic processes involving alkyl radicals as intermediates. 相似文献
43.
Dr. Maria A. Antunes Joana T. Coutinho Dr. Isabel C. Santos Dr. Joaquim Marçalo Prof. Manuel Almeida José J. Baldoví Dr. Laura C. J. Pereira Dr. Alejandro Gaita‐Ariño Prof. Eugenio Coronado 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17817-17826
A tetravalent uranium compound with a radical azobenzene ligand, namely, [{(SiMe2NPh)3‐tacn}UIV(η2‐N2Ph2.)] ( 2 ), was obtained by one‐electron reduction of azobenzene by the trivalent uranium compound [UIII{(SiMe2NPh)3‐tacn}] ( 1 ). Compound 2 was characterized by single‐crystal X‐ray diffraction and 1H NMR, IR, and UV/Vis/NIR spectroscopy. The magnetic properties of 2 and precursor 1 were studied by static magnetization and ac susceptibility measurements, which for the former revealed single‐molecule magnet behaviour for the first time in a mononuclear UIV compound, whereas trivalent uranium compound 1 does not exhibit slow relaxation of the magnetization at low temperatures. A first approximation to the magnetic behaviour of these compounds was attempted by combining an effective electrostatic model with a phenomenological approach using the full single‐ion Hamiltonian. 相似文献
44.
Investigations of the Vicarious C‐Aminations of 5,7‐Dinitrobenzotriazole and 4,6‐Dinitrobenzotriazol‐3‐ium‐1‐oxide and Their Energetic Properties 下载免费PDF全文
Dieter Ehlers Prof. Dr. Thomas M. Klapötke Carolin Pflüger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(45):16073-16082
This combined experimental and theoretical study details the vicarious nucleophilic substitution by amination of 5,7‐dinitrobenzotriazol ( 1 ) and 4,6‐dinitrobenzotriazole‐3‐ium‐1‐oxide ( 4 ) with trimethylhydrazinium iodide to afford the new corresponding one‐ and two‐time aminated compounds and investigations of its mechanism by EPR spectroscopy. The preferred position for the first amination is computed by spin density population and verified by X‐ray crystallography. The zwitterionic structure of 4 is investigated in solution by 1H NMR spectroscopy and in solid state by X‐ray diffraction. Furthermore, the crystal structure of 1 is presented. The energetic behavior of the aminated products as well as the starting materials 1 and 4 was investigated, regarding sensitivities and performance. 相似文献
45.
Vanessa C. Lussini Dr. James P. Blinco Dr. Kathryn E. Fairfull‐Smith Prof. Steven E. Bottle 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(50):18258-18268
Novel profluorescent mono‐ and bis‐isoindoline nitroxides linked to napthalimide and perylene diimide structural cores are described. These nitroxide‐fluorophore probes display strongly suppressed fluorescence in comparison to their corresponding non‐radical diamagnetic methoxyamine derivatives. The perylene‐based probe possessing two isoindoline systems tethered through ethynyl linkages was shown to be the most photostable in solution, demonstrating significantly enhanced longevity over the 9,10‐bis(phenylethynyl)anthracene fluorophore used in previous profluorescent nitroxide probes. 相似文献
46.
Dr. Xiao‐Jun Tang Zuxiao Zhang Prof. Dr. William R. Dolbier Jr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(52):18961-18965
Photoredox‐catalyzed reductive difluoromethylation of electron‐deficient alkenes was achieved in one step under tin‐free, mild and neutral conditions. This protocol affords a facile method to introduce RCF2 (R=H, Ph, Me, and CH2N3) groups at sites β to electron‐withdrawing groups. It was found that TTMS (tris(trimethylsilyl)silane) served nicely as both the H‐atom donor and the electron donor in the catalytic cycle. Experimental and DFT computational results provided evidence that RCF2 (R=H, Ph, Me) radicals are nucleophilic in nature. 相似文献
47.
Dr. Lin He Dr. Kishore Natte Dr. Jabor Rabeah Dr. Christoph Taeschler Dr. Helfried Neumann Prof. Dr. Angelika Brückner Prof. Dr. Matthias Beller 《Angewandte Chemie (International ed. in English)》2015,54(14):4320-4324
Fluorinated organic compounds are gaining increasing interest for life science applications. The replacement of hydrogen in arenes or heteroarenes by a perfluoroalkyl group has a profound influence on the physical and biological properties of such building blocks. Here, an operationally simple protocol for the direct C? H perfluoroalkylation of (hetero)arenes with RfI or RfBr has been developed, using a robust supported platinum catalyst. The ready availability of the starting materials, the excellent substrate tolerance, and the reusability of the catalyst make this method attractive for the synthesis of a variety of perfluoroalkyl‐substituted aromatic compounds. Preliminary mechanistic studies revealed the formation of radicals to be crucial in the reaction system. 相似文献
48.
Visible‐Light‐Promoted Iminyl‐Radical Formation from Acyl Oximes: A Unified Approach to Pyridines,Quinolines, and Phenanthridines 下载免费PDF全文
Heng Jiang Xiaode An Kun Tong Tianyi Zheng Prof. Dr. Yan Zhang Prof. Dr. Shouyun Yu 《Angewandte Chemie (International ed. in English)》2015,54(13):4055-4059
A unified strategy involving visible‐light‐induced iminyl‐radical formation has been established for the construction of pyridines, quinolines, and phenanthridines from acyl oximes. With fac‐[Ir(ppy)3] as a photoredox catalyst, the acyl oximes were converted by 1 e? reduction into iminyl radical intermediates, which then underwent intramolecular homolytic aromatic substitution (HAS) to give the N‐containing arenes. These reactions proceeded with a broad range of substrates at room temperature in high yield. This strategy of visible‐light‐induced iminyl‐radical formation was successfully applied to a five‐step concise synthesis of benzo[c]phenanthridine alkaloids. 相似文献
49.
Inside Cover: Interception of Cobalt‐Based Carbene Radicals with α‐Aminoalkyl Radicals: A Tandem Reaction for the Construction of β‐Ester‐γ‐amino Ketones (Angew. Chem. Int. Ed. 4/2015) 下载免费PDF全文
50.
Redox‐Neutral α‐Allylation of Amines by Combining Palladium Catalysis and Visible‐Light Photoredox Catalysis 下载免费PDF全文
Jun Xuan Ting‐Ting Zeng Zhu‐Jia Feng Qiao‐Hui Deng Prof. Dr. Jia‐Rong Chen Dr. Liang‐Qiu Lu Prof. Dr. Wen‐Jing Xiao Prof. Dr. Howard Alper 《Angewandte Chemie (International ed. in English)》2015,54(5):1625-1628
An unprecedented α‐allylation of amines was achieved by combining palladium catalysis and visible‐light photoredox catalysis. In this dual catalysis process, the catalytic generation of allyl radical from the corresponding π‐allylpalladium intermediate was achieved without additional metal reducing reagents (redox‐neutral). Various allylation products of amines were obtained in high yields through radical cross‐coupling under mild reaction conditions. Moreover, the transformation was applied to the formal synthesis of 8‐oxoprotoberberine derivatives which show potential anticancer properties. 相似文献