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971.
Mechanistic Insights into the Ni‐Catalyzed Reductive Carboxylation of C−O Bonds in Aromatic Esters with CO2: Understanding Remarkable Ligand and Traceless‐Directing‐Group Effects 下载免费PDF全文
Yan‐Li Han Bing‐Yuan Zhao Kun‐Yao Jiang Hui‐Min Yan Dr. Zhu‐Xia Zhang Dr. Wen‐Jing Yang Prof. Dr. Zhen Guo Prof. Dr. Yan‐Rong Li 《化学:亚洲杂志》2018,13(12):1570-1581
The mechanism of the Ni0‐catalyzed reductive carboxylation reaction of C(sp2)?O and C(sp3)?O bonds in aromatic esters with CO2 to access valuable carboxylic acids was comprehensively studied by using DFT calculations. Computational results revealed that this transformation was composed of several key steps: C?O bond cleavage, reductive elimination, and/or CO2 insertion. Of these steps, C?O bond cleavage was found to be rate‐determining, and it occurred through either oxidative addition to form a NiII intermediate, or a radical pathway that involved a bimetallic species to generate two NiI species through homolytic dissociation of the C?O bond. DFT calculations revealed that the oxidative addition step was preferred in the reductive carboxylation reactions of C(sp2)?O and C(sp3)?O bonds in substrates with extended π systems. In contrast, oxidative addition was highly disfavored when traceless directing groups were involved in the reductive coupling of substrates without extended π systems. In such cases, the presence of traceless directing groups allowed for docking of a second Ni0 catalyst, and the reactions proceed through a bimetallic radical pathway, rather than through concerted oxidative addition, to afford two NiI species both kinetically and thermodynamically. These theoretical mechanistic insights into the reductive carboxylation reactions of C?O bonds were also employed to investigate several experimentally observed phenomena, including ligand‐dependent reactivity and site‐selectivity. 相似文献
972.
Visible‐Light‐Driven Chemoselective Hydrogenation of Nitroarenes to Anilines in Water through Graphitic Carbon Nitride Metal‐Free Photocatalysis 下载免费PDF全文
Green and efficient procedures are essential for the chemoselective hydrogenation of functionalized nitroarenes to form industrially important anilines. Herein, it is shown that visible‐light‐driven, chemoselective hydrogenation of functionalized nitroarenes with groups sensitive to forming anilines can be achieved in good to excellent yields (82–100 %) in water under relatively mild conditions and catalyzed by low‐cost and recyclable graphitic carbon nitride. The process is also applicable to gram‐scale reaction, with a yield of aniline of 86 %. A study of the mechanism reveals that visible‐light‐induced electrons are responsible for the hydrogenation reactions, and thermal energy can also promote the photocatalytic activity. A study of the kinetics shows that this reaction possibly occurs through one‐step hydrogenation or stepwise condensation routes. A wide range of applications can be expected for this green, efficient, and highly selective photocatalysis system in reduction reactions for the synthesis of fine chemicals. 相似文献
973.
Dr. Rud Wegscheider 《Monatshefte für Chemie / Chemical Monthly》1895,16(1):153-158
Ohne Zusammenfassung 相似文献
974.
Dr. August Chwala 《Colloid and polymer science》1931,56(1):117-122
Ohne Zusammenfassung 相似文献
975.
976.
J. G. C. M. van Duijneveldt-van de Rijdt Dr. F. B. van Duijneveldt 《Theoretical chemistry accounts》1970,19(1):83-91
Using perturbation theory of intermolecular forces (including exchange effects) hydrogen-bond energies are calculated for a simple model representing the water dimer. Several orientations of the proton acceptor with respect to the O...O axis are considered and it is found that the optimum orientation depends sensitively on the oxygen lone-pair hybridization assumed. The main orientation-dependent energy term is found to be the classical electrostatic energy between the unperturbed molecules. The relation of the present results to the structures of the ices I and Ic, and to the results of recent SCF studies are discussed briefly.
For some recent CNDO/2 calculations on (H2O)2 which concentrate mainly on rotations of the donor see Ref. [5]. 相似文献
Zusammenfassung Die Energien von Wasserstoffbindungen werden für ein einfaches Modell des dimeren Wassers mit Hilfe der Störungstheorie für intermolekulare Kräfte (mit Austauscheffekten) berechnet. Verschiedene Orientierungen des Protonen-Akzeptors bezüglich der O ... O-Achse werden untersucht; man findet, daß die optimale Orientierung empfindlich von der angenommen Hybridisierung des einsamen Elektronenpaars des Sauerstoffs abhängt. Der hauptsächliche, von der Orientierung abhängige Energieterm ist die klassische elektrostatische Energie zwischen den beiden ungestörten Molekülen. Die Beziehung der vorliegenden Ergebnisse zu den Strukturen von Eis I und Ic sowie zu den Ergebnissen kürzlicher SCF-Rechnungen wird kurz diskutiert.
For some recent CNDO/2 calculations on (H2O)2 which concentrate mainly on rotations of the donor see Ref. [5]. 相似文献
977.
Summary Previous studies have indicated that non-ionic surface active agents, such as n-dodecylhexaoxyethylene glycol monoether, confer considerable protection on silver iodide sols to flocculation by inorganic cations. In the present study the effects of hydrolysis of the flocculating cations, lanthanum, aluminium and thorium have been examined. It was found that with the hydrolysed cations the protective action of the non-ionic surface active agent was considerably diminished. It was deduced that the hydrolysed species are more strongly adsorbed than the nonionic surface active agent and either displace the latter from the surface or form species which are large enough to cause flocculation by interparticle bridging.
With 6 figures and 1 table 相似文献
Zusammenfassung Vorausgehende Untersuchungen haben gezeigt, daß nichtionische oberflächenaktive Substanzen wie n-Dodecylhexaoxyäthylen-glykol-monoäther beträchtliche Schutzwirkung Silberjodidsolen gegenüber Flokkung durch anorganische Kationen verleihen. In der vorliegenden Untersuchung wird die Wirkung der Hydrolyse flockender Kationen, Lanthan, Aluminium und Thorium, geprüft. Es wurde gefunden, daß durch die hydrolisierten Kationen die Schutzwirkung der nichtionischen oberflächenaktiven Substanz beträchtlich vermindert wird. Daraus ist zu schließen, daß die hydrolisierte Ionenart stärker als das nichtoberflächenaktive Agens adsorbiert wird und deshalb das letztere von der Oberfläche entfernt wird oder genügend große interpartikuläre Brücken, bildet, um Flockung zu verursachen.
With 6 figures and 1 table 相似文献
978.
Dr. Theodor N. Kleinert Dr. Roderick E. Townshend 《Monatshefte für Chemie / Chemical Monthly》1970,101(2):375-379
Zusammenfassung Die beim Verstrecken sowie Mahlen von künstlichen organischen Fasermaterialien (Polyester-, Polyamid- und Viskosefasern) als Folge homolytischer Kettenspaltungen auftretende Freiradikalbildung wurde untersucht.
Mit 3 Abbildungen
Die Elektronspinresonanz-Messungen wurden im Chemischen Institut der Sir George Williams University, Montreal, Canada, durchgeführt. 相似文献
Mechanochemical reactions in synthetic organic fibres
The formation of free radicals due to homolytic chain fission occurring in the course of stretching and grinding of synthetic organic fibres (polyester, polyamide, and viscose fibres) has been investigated by means of ESR spectroscopy.
Mit 3 Abbildungen
Die Elektronspinresonanz-Messungen wurden im Chemischen Institut der Sir George Williams University, Montreal, Canada, durchgeführt. 相似文献
979.
Jinhua Wang Dr. Barbara Wicher Dr. Victor Maurizot Prof. Ivan Huc 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(3):1031-1038
Quinoline based aromatic amide foldamers are known to adopt stable folded conformations. We have developed a synthetic approach to produce similar oligomers where all amide bonds, or part of them, have been replaced by an isosteric vinylene group. The results of solution and solid state structural studies show that oligomers exclusively containing vinylene linkages are not well folded, and adopt predominantly flat conformations. In contrast, a vinylene segment flanked by helical oligoamides also folds in a helix, albeit with a slightly lower curvature. The presence of vinylene functions also result in an extension of π-conjugation across the oligomer that may change charge transport properties. Altogether, these results pave the way to foldamers in which both structural control and specific electronic properties may be engineered. 相似文献
980.
Yang Min Dr. Chuandong Dou Prof. Hongkun Tian Prof. Jun Liu Prof. Lixiang Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(13):4364-4372
The B←N unit has a large dipole and it is isoelectronic to C−C moiety with no dipole. Incorporating B←N units into π-conjugated system is a powerful strategy to design organic small molecules and polymers with intriguing opto-electronic properties and excellent opto-electronic device performance. However, it is unclear how the B←N unit affects electronic structures and opto-electronic properties of large π-conjugated molecules. In this work, to address this question, we developed three dibenzo-azaacene molecules in which two B←N units were introduced at different positions. Although the dibenzo-azaacene skeleton is fully π-conjugated, the effect of B←N unit on the electronic structures of the adjacent rings is much stronger than that of the distant rings. As a result, the three molecules with isomerized B←N incorporation patterns possess different electronic structures and exhibit tunable opto-electronic properties. Among the three molecules, the centrosymmetrical molecule exhibits higher LUMO/HOMO energy levels than those of the two axisymmetrical molecules. When used as the active layer in organic field-effect transistors (OFETs), while the two axisymmetrical molecules show unipolar electron transporting property, the centrosymmetrical molecule exhibits ambipolar hole and electron transporting behavior. This work not only deepens our understanding on organoboron π-conjugated molecules, but also indicates a new strategy to tune opto-electronic properties of organic semiconductors for excellent device performance. 相似文献