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231.
Guangcan Xu Sbastien Leloux Pinglu Zhang Jorge Meijide Surez Yongmin Zhang Etienne Derat Mickaël Mnand Olivia Bistri‐Aslanoff Sylvain Roland Tom Leyssens Olivier Riant Matthieu Sollogoub 《Angewandte Chemie (International ed. in English)》2020,59(19):7591-7597
The encapsulation of copper inside a cyclodextrin capped with an N‐heterocyclic carbene (ICyD) allowed both to catch the elusive monomeric (L)CuH and a cavity‐controlled chemoselective copper‐catalyzed hydrosilylation of α,β‐unsaturated ketones. Remarkably, (α‐ICyD)CuCl promoted the 1,2‐addition exclusively, while (β‐ICyD)CuCl produced the fully reduced product. The chemoselectivity is controlled by the size of the cavity and weak interactions between the substrate and internal C?H bonds of the cyclodextrin. 相似文献
232.
Jos I. Urgel Marco Di Giovannantonio Kristjan Eimre Thorsten G. Lohr Junzhi Liu Shantanu Mishra Qiang Sun Amogh Kinikar Roland Widmer Samuel Stolz Max Bommert Reinhard Berger Pascal Ruffieux Carlo A. Pignedoli Klaus Müllen Xinliang Feng Roman Fasel 《Angewandte Chemie (International ed. in English)》2020,59(32):13281-13287
Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on‐surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well‐controlled ultrahigh‐vacuum conditions. Here we report the on‐surface synthesis of a polymer linked by cumulene‐like bonds on a Au(111) surface via sequential thermally activated dehalogenative C?C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene‐like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X‐ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on‐surface synthesis of cumulene‐containing compounds, as well as protocols relevant to the stepwise fabrication of carbon–carbon bonds on surfaces. 相似文献
233.
Samuel Stolz Marco Di Giovannantonio Jos I. Urgel Qiang Sun Amogh Kinikar Gabriela Borin Barin Max Bommert Roman Fasel Roland Widmer 《Angewandte Chemie (International ed. in English)》2020,59(33):14106-14110
In the emerging field of on‐surface synthesis, dehalogenative aryl–aryl coupling is unarguably the most prominent tool for the fabrication of covalently bonded carbon‐based nanomaterials. Despite its importance, the reaction kinetics are still poorly understood. Here we present a comprehensive temperature‐programmed x‐ray photoelectron spectroscopy investigation of reaction kinetics and energetics in the prototypical on‐surface dehalogenative polymerization of 4,4′′‐dibromo‐p‐terphenyl into poly(para‐phenylene) on two coinage metal surfaces, Cu(111) and Au(111). We find clear evidence for reversible dehalogenation on Au(111), which is inhibited on Cu(111) owing to the formation of organometallic intermediates. The incorporation of reversible dehalogenation in the reaction rate equations leads to excellent agreement with experimental data and allows extracting the relevant energy barriers. Our findings deepen the mechanistic understanding and call for its reassessment for surface‐confined aryl–aryl coupling on the most frequently used metal substrates. 相似文献
234.
Jacques Penelle Vronique Mayn Roland Touillaux 《Journal of polymer science. Part A, Polymer chemistry》1996,34(16):3369-3378
2-(Trimethylsiloxy)butadiene (TMSBD) and 2-(tert-butyldimethylsiloxy)butadiene (TBMSBD) were copolymerized with styrene (St) and methyl methacrylate (MMA) under free-radical conditions. The obtained polymers were found to contain reactive silyl enol ether groups in a ratio identical to the TMSBD or TBMSBD molar fraction in the copolymer. All investigated samples displayed only 1,4- and 3,4-microstructures. The influence of several experimental factors on the yields, rates of polymerization, microstructures, and copolymer compositions were examined. Monomer reactivity ratios r1 and r2 at 60°C were determined from copolymer composition curves at low conversions. The homopolymerization of TBMSBD was also investigated and results were compared with those previously obtained for TMSBD. A slight increase in rates was observed and was rationalized on the basis of the higher viscosity resulting from the structural change in the monomer. Thermal stabilities of the synthesized polymers were investigated by TGA and their glass transition temperatures were determined by DSC. All measurements are compatible with a possible use of TMSBD and TBMSBD copolymers as reactive polymers. © 1996 John Wiley & Sons, Inc. 相似文献
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236.
Roland Full 《Chemie in Unserer Zeit》1996,30(6):286-294
Overhead projection with supplementary lenses provides „wallfilling big screen”︁ detailed pictures of physical and chemical phenomena and thus helps to train chemists to make accurate observations, comparisons, and interpretations. By using divided petri dishes, it is possible to present parallel and control experiments with minimal amounts of substances in one field of vision, and thus to establish the links between substance and reaction, and formula and equation. In particular, for the demonstration of electrochemical processes, the divided petri dish proves to be a projectable minimal system, which is characterized by maximum economy and ecology. Great recognition with little substance?. 相似文献
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The continuous miniaturization in microelectronics requires advanced materials and processes. Novel specifically functionalized anhydride-containing filmforming polymers which spontaneously react with bisaminoalkylsiloxanes were synthesized for use in photolithographic processes. This allows the modelling of photoresist patterns and thus enhancement of practical resolution. In addition, efficient polymeric dielectrics with improved solubility in environmentally safe solvents were developed. The latter can be patterned using the above mentioned photolithographic process. 相似文献