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61.
Cage‐like Copper(II) Silsesquioxanes: Transmetalation Reactions and Structural,Quantum Chemical,and Catalytic Studies
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Dr. Alexey N. Bilyachenko Dr. Marina S. Dronova Alexey I. Yalymov Dr. Frédéric Lamaty Dr. Xavier Bantreil Prof. Jean Martinez Christelle Bizet Lidia S. Shul'pina Prof. Alexander A. Korlyukov Dmitry E. Arkhipov Dr. Mikhail M. Levitsky Prof. Elena S. Shubina Dr. Alexander M. Kirillov Prof. Georgiy B. Shul'pin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(24):8758-8770
The transmetalation of bimetallic copper–sodium silsesquioxane cages, namely, [(PhSiO1.5)10(CuO)2(NaO0.5)2] (“Cooling Tower”; 1 ), [(PhSiO1.5)12(CuO)4(NaO0.5)4] (“Globule”; 2 ), and [(PhSiO1.5)6(CuO)4(NaO0.5)4(PhSiO1.5)6] (“Sandwich”; 3 ), resulted in the generation of three types of hexanuclear cylinder‐like copper silsesqui‐ oxanes, [(PhSiO1.5)12(CuO)6(C4H9OH)2(C2H5OH)6] ( 4 ), [(PhSiO1.5)12(CuO)6(C4H8O2)4(PhCN)2(MeOH)4] ( 5 ), and [(PhSiO1.5)12(CuO)6(NaCl)(C4H8O2)12(H2O)2] ( 6 ). The products show a prominent “solvating system–structure” dependency, as determined by X‐ray diffraction. Topological analysis of cages 1 – 6 was also performed. In addition, DFT theory was used to examine the structures of the Cooling Tower and Cylinder compounds, as well as the spin density distributions. Compounds 1 , 2 , and 5 were applied as catalysts for the direct oxidation of alcohols and amines into the corresponding amides. Compound 6 is an excellent catalyst in the oxidation reactions of benzene and alcohols. 相似文献
62.
The reaction of iron sulfate with 1-carboxymethyl-4,7-dimethyl-1,4,7-triazacyclononane (L) and hydrogen peroxide in aqueous ethanol gives a brown dinuclear complex considered to be [Fe2(N3O-L)2(mu-O)(mu-OOCCH3)] + (1), which converts upon standing in acetonitrile solution into the green tetranuclear complex [Fe4(N3O2-L)4(mu-O)2]4+ (2). A single-crystal X-ray structure analysis of [2][PF6]4.5MeCN reveals 2 to contain four iron(III) centers, each of which is coordinated to three nitrogen atoms of a triazacyclononane ligand and is bridged by one oxo and two carboxylato bridges, a structural feature known from the active center of methane monooxygenase. Accordingly, complex 2 was found to catalyze the oxidative functionalization of methane with hydrogen peroxide in aqueous solution to give methanol, methyl hydroperoxide, and formic acid; the total turnover numbers attain 24 catalytic cycles within 4 h. To gain more insight into the catalytic process, the catalytic potential of 2 was also studied for the oxidation of higher alkanes, cycloalkanes, and isopropanol in acetonitrile, as well as in aqueous solution. The bond selectivities of the oxidation of linear and branched alkanes suggest a ferroxy radical pathway. 相似文献
63.
Five new 1,4,7-triazacyclononane-derived compounds, sodium 3-(4,7-dimethyl-1,4,7-triazacyclononan-1-yl)propionate (Na[LMe2R']) as well as the enantiopure derivatives (S)-1-(2-methylbutyl)-4,7-dimethyl-1,4,7-triazacyclononane (S-LMe2R'), SS-trans-2,5,8-trimethyl-2,5,8-triazabicyclo[7.4.01,9]tridecane (SS-LBMe3), (S)-1-(2-hydroxypropyl)-4,7-dimethyl-1,4,7-triazacyclononane (S-LMe2R), and (R)-1-(2-hydroxypropyl)-4,7-dimethyl-1,4,7-triazacyclononane (R-LMe2R), have been synthesized. Reaction of manganese dichloride with the chiral macrocycles S-LMe2R and R-LMe2R in aqueous ethanol gives, upon oxidation with hydrogen peroxide, the brown dinuclear Mn(III)-Mn(IV) complexes which are enantiomers, [Mn2(S-LMe2R)2(mu-O)2]3+ (S,S-1) and [Mn2(R-LMe2R)2(mu-O)2]3+ (R,R-1). The single-crystal X-ray structure analyses of [S,S-1][PF6]3.0.5(CH3)2CO and [R,R-1][PF6]3.0.5(CH3)2CO show both enantiomers to contain Mn(III) and Mn(IV) centers, each of which being coordinated to three nitrogen atoms of a triazacyclononane ligand and each of which being bridged by two oxo and by two chiral hydroxypropyl pendent arms of the macrocycle. The enantiomeric complexes S,S-1 and R,R-1 were found to catalyze the oxidation of olefins, alkanes, and alcohols with hydrogen peroxide. In the epoxidation of indene the enantiomeric excess values attain 13%. The bond selectivities of the oxidation of linear and branched alkanes suggest the crucial step in this process to be the attack of a sterically hindered high-valent manganese-oxo species on the C-H bond. 相似文献
64.
Anton N. Lukoyanov Iakov S. Fomenko Marko I. Gongola Lidia S. Shulpina Nikolay S. Ikonnikov Georgiy B. Shulpin Sergey Y. Ketkov Georgy K. Fukin Roman V. Rumyantcev Alexander S. Novikov Vladimir A. Nadolinny Maxim N. Sokolov Artem L. Gushchin 《Molecules (Basel, Switzerland)》2021,26(18)
A new monoiminoacenaphthenone 3,5-(CF3)2C6H3-mian (complex 2) was synthesized and further exploited, along with the already known monoiminoacenaphthenone dpp-mian, to obtain oxidovanadium(IV) complexes [VOCl2(dpp-mian)(CH3CN)] (3) and [VOCl(3,5-(CF3)2C6H3-bian)(H2O)][VOCl3(3,5-(CF3)2C6H3-bian)]·2.85DME (4) from [VOCl2(CH3CN)2(H2O)] (1) or [VCl3(THF)3]. The structure of all compounds was determined using X-ray structural analysis. The vanadium atom in these structures has an octahedral coordination environment. Complex 4 has an unexpected structure. Firstly, it contains 3,5-(CF3)2C6H3-bian instead of 3,5-(CF3)2C6H3-mian. Secondly, it has a binuclear structure, in contrast to 3, in which two oxovanadium parts are linked to each other through V=O···V interaction. This interaction is non-covalent in origin, according to DFT calculations. In structures 2 and 3, non-covalent π-π staking interactions between acenaphthene moieties of the neighboring molecules (distances are 3.36–3.40 Å) with an estimated energy of 3 kcal/mol were also found. The redox properties of the obtained compounds were studied using cyclic voltammetry in solution. In all cases, the reduction processes initiated by the redox-active nature of the mian or bian ligand were identified. The paramagnetic nature of complexes 3 and 4 has been proven by EPR spectroscopy. Complexes 3 and 4 exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The yields of products of cyclohexane oxidation were 43% (complex 3) and 27% (complex 4). Based on the data regarding the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play the most crucial role in the reaction. The initial products in the reactions with alkanes are alkyl hydroperoxides, which are easily reduced to their corresponding alcohols by the action of triphenylphosphine (PPh3). According to the DFT calculations, the difference in the catalytic activity of 3 and 4 is most likely associated with a different mechanism for the generation of ●OH radicals. For complex 4 with electron-withdrawing CF3 substituents at the diimine ligand, an alternative mechanism, different from Fenton’s and involving a redox-active ligand, is assumed. 相似文献
65.
Konstantin V. Savateev Victor V. Fedotov Vladimir L. Rusinov Svetlana K. Kotovskaya Alexandr A. Spasov Aida F. Kucheryavenko Pavel M. Vasiliev Vadim A. Kosolapov Victor S. Sirotenko Kseniya A. Gaidukova Georgiy M. Uskov 《Molecules (Basel, Switzerland)》2022,27(1)
Hypercytokinemia, or cytokine storm, is one of the severe complications of viral and bacterial infections, involving the release of abnormal amounts of cytokines, resulting in a massive inflammatory response. Cytokine storm is associated with COVID-19 and sepsis high mortality rate by developing epithelial dysfunction and coagulopathy, leading to thromboembolism and multiple organ dysfunction syndrome. Anticoagulant therapy is an important tactic to prevent thrombosis in sepsis and COVID-19, but recent data show the incompatibility of modern direct oral anticoagulants and antiviral agents. It seems relevant to develop dual-action drugs with antiviral and anticoagulant properties. At the same time, it was shown that azolo[1,5-a]pyrimidines are heterocycles with a broad spectrum of antiviral activity. We have synthesized a new family of azolo[1,5-a]pyrimidines and their condensed polycyclic analogs by cyclocondensation reactions and direct CH-functionalization and studied their anticoagulant properties. Five compounds among 1,2,4-triazolo[1,5-a]pyrimidin-7-ones and 5-alkyl-1,3,4-thiadiazolo[3,2-a]purin-8-ones demonstrated higher anticoagulant activity than the reference drug, dabigatran etexilate. Antithrombin activity of most active compounds was confirmed using lipopolysaccharide (LPS)-treated blood to mimic the conditions of cytokine release syndrome. The studied compounds affected only the thrombin time value, reliably increasing it 6.5–15.2 times as compared to LPS-treated blood. 相似文献
66.
Trusova VM Kirilova E Kalnina I Kirilov G Zhytniakivska OA Fedorov PV Gorbenko GP 《Journal of fluorescence》2012,22(3):953-959
The potential of novel benzanthrone aminoderivatives to trace the changes in physicochemical properties of lipid bilayer has
been evaluated. Binding of the dyes to the lipid bilayers composed of zwitterionic phospholipid phosphatidylcholine (PC) and
its mixtures with anionic phospholipid cardiolipin (CL) and cholesterol (Chol) was followed by significant quantum yield increase
with small blue shift of emission maximum. Analysis of partition coefficients of the dyes under study showed that all aminobenzanthrones
possess high lipid-associating ability. The dyes A8 and AM2 proved to be sensitive to the variations in membrane chemical
composition responding to the changes in bilayer hydration induced by CL and Chol. 相似文献
67.
Gopi K. Samudrala Georgiy Tsoi Andrei V. Stanishevsky Jeffrey M. Montgomery Samuel T. Weir 《高压研究》2013,33(3):388-398
Epitaxial boron-doped diamond films were grown by microwave plasma chemical vapor deposition for application as heating elements in high pressure diamond anvil cell devices. To a mixture of hydrogen, methane and oxygen, diborane concentrations of 240–1200 parts per million were added to prepare five diamond thin-film samples. Surface morphology has been observed to change depending on the amount of diborane added to the feed gas mixture. Single-crystal diamond film with a lowest room temperature resistivity of 18 mΩ cm was fabricated and temperature variation of resistivity was studied to a low temperature of 12 K. The observed minima in resistivity values with temperature for these samples have been attributed to a change in conduction mechanism from band conduction to hopping conduction. We also present a novel fabrication methodology for monocrystalline electrically conducting channels in diamond and present preliminary heating data with a boron-doped designer diamond anvil to 620 K at ambient pressure. 相似文献
68.
Magnetic ordering temperatures in heavy rare earth metal dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to a pressure of 69 GPa and a temperature of 10 K. Previous studies using magnetic susceptibility measurements at high pressures were able to track magnetic ordering temperature only till 7 GPa in the hexagonal close packed (hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. This is followed by a rapid increase in the magnetic ordering temperatures in the double hcp phase and finally leveling off in the distorted face centered cubic phase of Dy. Our studies reaffirm that 4f-shell remains localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa. 相似文献
69.
Hashorva Enkelejd Mishura Yuliya Shevchenko Georgiy 《Journal of Theoretical Probability》2021,34(2):728-754
Journal of Theoretical Probability - We study boundary non-crossing probabilities $$\begin{aligned} P_{f,u} := \mathrm {P}\big (\forall t\in {\mathbb {T}}\ X_t + f(t)\le u(t)\big ) \end{aligned}$$... 相似文献
70.
Taras O. Banakh Fedor A. Bogomolov Andrij I. Gatalevych Ihor J. Guran Yurij B. Ishchuk Mykola Ya. Komarnytskyi Igor S. Kuz Ivanna O. Melnyk Vasyl M. Petrychkovych Yaroslav G. Prytula Oleh M. Romaniv Oleh B. Skaskiv Ludmyla L. Stakhiv Georgiy T. Sullym Bohdan V. Zabavskyi Volodymir P. Zelisko Mykhajlo M. Zarichnyi 《Central European Journal of Mathematics》2013,11(9):1547-1551