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81.
Observation that rates of dehydrobromination of trans-β-bromostyrene (1) and the Hofmann degradation of tetrabutyl ammonium cation depend on strength of base in different ways and that treatment of 1 with base results in fast abstraction of the β-proton imply the possibility that the dehydrobromination of 1 could proceed via α-elimination and Ph migration. In order to clarify this question, β-13C-labeled 1 was obtained and subjected to PTC dehydrobromination which proceeds without migration of Ph. The obtained results are consistent with an irreversible E1cB mechanism. 相似文献
82.
Alexey N. Egorochkin Nadiya M. Khamaletdinova 《Journal of organometallic chemistry》2011,696(10):2199-2205
The literature data on substituent influence on the CS, CN, NC, NN, and NO stretching frequencies (ν) in the IR spectra and in specific cases on their respective stretching force constants (k) have been analyzed for 28 series of the transition metal complexes. The ν and k values were first established to depend not only on the inductive and resonance effects but on the polarizability of substituents as well. The contribution of the polarizability effect varies from 0 to 57% with the type of series. 相似文献
83.
A many-particle, in the general case, inhomogeneous reacting system of independent pairs of reactants, where geminate reversible reaction A+B?C takes place, is considered in the framework of the kinetic theory approach. The kinetic equations in the thermodynamic limit are obtained, and important relations between kinetic coefficients characterizing the reaction course are established, as well as the relations between the kinetic dependencies under different initial conditions including the relations that extend the familiar literature results to the case of rather realistic model of the reacting system. Universal long-term kinetic laws of the reaction course are determined. 相似文献
84.
Michael A. Pudovik Lyudmila Kibardina Alexey Trifonov Alexey Dobrynin Sergei Katsyuba Alexander Burilov 《Phosphorus, sulfur, and silicon and the related elements》2019,194(1-2):120-126
New O-phosphorylated pyridoxal derivatives have been synthesized through the reaction of azomethines with РV acid chlorides. 2-Chloro-2-thioxo-5,5-dimethyl-1,3,2-dioxaphosphinanes and diethylchlorothiophosphate have been employed as phosphorylating agents. Regardless of the nature of the phosphorylating agent, the reaction is regioselective at phenolic hydroxyl group. The structure of final products is determined by the nature of the substituent at the nitrogen atom. If R is alkyl or cycloalkyl group, the products of the reaction represent phosphorylated pyridoxal imines, whereas phosphorylated furopyridines are formed in the case R is aryl substituent. 相似文献
85.
Dmitry I. Bugaenko Alexey A. Volkov Dr. Mikhail V. Livantsov Prof. Dr. Marina A. Yurovskaya Dr. Alexander V. Karchava 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(54):12502-12506
The visible-light-induced arylation of tertiary phosphines with aryl(mesityl)iodonium triflates to produce the quaternary phosphonium salts occurs under mild, metal, and catalyst-free conditions. Photo-excited EDA complexes between diaryliodonium salts and phosphines supposedly enable this transformation, which is difficult to achieve through the traditional ground-state reactions. Demonstrating high functional group tolerance, broad scope, and complete selectivity of the aryl group transfer, the method is particularly compatible with sterically congested phosphines, which are challenging under metal-based catalytic methods. 相似文献
86.
Dr. Alexey S. Kiryutin Mikhail S. Panov Dr. Alexandra V. Yurkovskaya Prof. Dr. Konstantin L. Ivanov Prof. Dr. Geoffrey Bodenhausen 《Chemphyschem》2019,20(5):766-772
A study of long-lived spin order in chlorothiophene carboxylates at both high and low magnetic fields is presented. Careful sample preparation (removal of dissolved oxygen in solution, chelating of paramagnetic impurities, reduction of convection) allows one to obtain very long-lived singlet order of the two coupled protons in chlorothiophene derivatives, having lifetimes of about 130 s in D2O and 240 s in deuterated methanol, which are much longer than the T1-relaxation times (18 and 30 s, respectively, at a field =9.4 T). In protonated solvents the relaxation times become shorter, but the lifetime is still substantially longer than . In addition, long-lived coherences are shown to have lifetimes as long as 30 s. Thiophene derivatives can be used as molecular tags to study slow transport, slow dynamics and slow chemical processes, as has been shown in recent years. 相似文献
87.
Alexey Bobrovsky Valery Shibaev Martin Cigl Vra Hamplov Vladimíra Novotn 《Journal of Polymer Science.Polymer Physics》2019,57(19):1337-1342
New photochromic polymethacrylates with different spacer length having azobenzene side groups and lateral methyl substituents were synthesized. The phase behavior of polymethacrylates and their photooptical properties were studied and compared with unsubstituted analogues. It is shown that an introduction of lateral methyl substituents results in almost complete suppression of liquid crystalline (LC) phase formation and strong decrease of photoinduced dichroism values. It is found that rates of the photoinduced E‐Z isomerization and back thermal Z‐E isomerization are almost independent on spacer lengths. Due to the presence of lateral substituents, the photoinduced azobenzene Z‐form shows remarkable long lifetime, and back thermal conversion at room temperature takes more than 10 days. Specific peculiarities of the photoorientation process in polymer films under the polarized UV and visible light action were studied and their mechanism is suggested. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1337–1342 相似文献
88.
Georgios Velkos Denis S. Krylov Kyle Kirkpatrick Lukas Spree Vasilii Dubrovin Bernd Büchner Stanislav M. Avdoshenko Valeriy Bezmelnitsyn Sean Davis Paul Faust James Duchamp Harry C. Dorn Alexey A. Popov 《Angewandte Chemie (International ed. in English)》2019,58(18):5891-5896
The azafullerene Tb2@C79N is found to be a single‐molecule magnet with a high 100‐s blocking temperature of magnetization of 24 K and large coercivity. Tb magnetic moments with an easy‐axis single‐ion magnetic anisotropy are strongly coupled by the unpaired spin of the single‐electron Tb?Tb bond. Relaxation of magnetization in Tb2@C79N below 15 K proceeds via quantum tunneling of magnetization with the characteristic time τQTM=16 462±1230 s. At higher temperature, relaxation follows the Orbach mechanism with a barrier of 757±4 K, corresponding to the excited states, in which one of the Tb spins is flipped. 相似文献
89.
90.
Xing Huang Detre Teschner Maria Dimitrakopoulou Alexey Fedorov Benjamin Frank Ralph Kraehnert Frank Rosowski Harry Kaiser Stephan Schunk Christiane Kuretschka Robert Schlgl Marc‐Georg Willinger Annette Trunschke 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(26):8801-8805
The direct conversion of syngas to ethanol, typically using promoted Rh catalysts, is a cornerstone reaction in CO2 utilization and hydrogen storage technologies. A rational catalyst development requires a detailed structural understanding of the activated catalyst and the role of promoters in driving chemoselectivity. Herein, we report a comprehensive atomic‐scale study of metal–promoter interactions in silica‐supported Rh, Rh–Mn, and Rh–Mn–Fe catalysts by aberration‐corrected (AC) TEM. While the catalytic reaction leads to the formation of a Rh carbide phase in the Rh–Mn/SiO2 catalyst, the addition of Fe results in the formation of bimetallic Rh–Fe alloys, which further improves the selectivity and prevents the carbide formation. In all promoted catalysts, Mn is present as an oxide decorating the metal particles. Based on the atomic insight obtained, structural and electronic modifications induced by promoters are revealed and a basis for refined theoretical models is provided. 相似文献