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排序方式: 共有1698条查询结果,搜索用时 218 毫秒
1.
Roberto Morales-Cerrada Dr. Christophe Fliedel Dr. Jean-Claude Daran Dr. Florence Gayet Dr. Vincent Ladmiral Dr. Bruno Améduri Prof. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):296-308
Thermal decarbonylation of the acyl compounds [Mn(CO)5(CORF)] (RF=CF3, CHF2, CH2CF3, CF2CH3) yielded the corresponding alkyl derivatives [Mn(CO)5(RF)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(12CO)4(eq-13CO)(RF)] and [Mn(12CO)4(ax-13CO)(RF)] isotopomers and a ranking of the RF donor power in the order CF3<CHF2<CH2CF3≈CF2CH3. The homolytic Mn−RF bond cleavage in [Mn(CO)5(RF)] at various temperatures under saturation conditions with trapping of the generated RF radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH≠ and ΔS≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−RF bond cleavage was further demonstrated by the observation that [Mn(CO)5(CF3)] (the compound with the strongest Mn−RF bond) initiated the radical polymerization of vinylidene fluoride (CH2=CF2) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation. 相似文献
2.
Stephen Butkewitsch 《Applied Surface Science》2006,252(23):8277-8286
The present study showed that sulfonated poly(styrene-ethylene/butylenes-styrene) (S-SEBS) triblock copolymer ionomers can be made to exhibit dielectric constants on the order of a hundreds thousand. Although they are too lossy at this point to use as dielectric materials in capacitors or as electrostrictive Maxwell effect transducer materials because of their high hydrogen ion conductivity, the results of these initial dielectric studies as a function of ion content were used to try to understand the effects of a polar plasticizer, water, on dielectric properties of the acid form of this ionomer. This was done before moving on to more tightly bound ions (rather than the hydrogen ions of the sulfonic acid groups used here) and to other polar, less mobile plasticizers (which also interact strongly with the ionic dipoles). The discovery of such high dielectric constants suggested the possibility that low dielectric loss versions of this type of polymer, as well as other members of the class known as ionomers, might find future applications as extremely high dielectric constant materials in capacitors or transducers. Experimental results for films with degrees of sulfonation on the order of 10% or more showed dielectric constants on the order of ?′ ∼ 100,000 but dielectric loss tangents near D = tan δ ∼ 0.3, when the materials were exposed to high humidity conditions. Experiments to determine the effects of water content on the material's dielectric response showed that water can easily move into and out of the films studied and that this transport behavior is strongly correlated to the relative humidity of the environment and to the degree of sulfonation. Water content, in this case, was thus the primary consideration when attempting to understand the observed high dielectric constants in films with degree of sulfonation greater than 5.5%. However, vacuum-dried films were, also, examined and observed to exhibit a dielectric constant on the order of 2 until the degree of sulfonation was greater than 11%. Above this value, the dielectric constant increased by approximately 100% to a value on the order of 4. 相似文献
3.
采用溶解-反应量热法在具有恒温环境的溶解-反应热量计内,测定了[Gd(Gly)4(Im)(H2O)](ClO4)3和[Y(Gly)4(Im)(H2O)](ClO4)3两种稀土甘氨酸咪唑配合物的标准生成焓分别为(-3 461.46 ±0.22) kJ·mol-1 和(-3 926.6±0.90) kJ·mol-1. 相似文献
4.
Zhaohui Wang 《Thermochimica Acta》2004,414(1):31-33
Microcalorimetric measurements of excess molar enthalpies, at 298.15 K, are reported for the four binary systems formed by mixing 1-hexene with the cycloalkanes: cyclohexane and methylcyclohexane, and with the aromatic hydrocarcons: benzene and toluene. Smooth Redlich-Kister representations of the results are presented. It was found that the Liebermann-Fried model also provided good representations of the results. 相似文献
5.
The enthalpies of formation of simple nonmetal or metalloid oxyanions in aqueous solution are discussed. Archival values are cited and estimates are made. Trends prove evasive. 相似文献
6.
B. V. Derjaguin 《Progress in Surface Science》1992,40(1-4):240-251
A review is presented about research on surface forces and surface interactions conducted over the past half-century, with some emphasis on the pioneering contributions of the Department of Surface Phenomena at the Institute of Physical Chemistry of the USSR Academy of Sciences. 相似文献
7.
The excess molar enthalpy of ternary mixture for 3-diethylaminopropylamine+heptane+cyclohexane were measured using a Calvet
microcalorimeter at 303.15 K.
Empirical equations, Redlich-Kister, Tsao-Smith, and Kohler and group contribution models, UNIFAC (modified version) and DISQUAC
have been applied. A reasonable representation of ternary data is obtained.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
8.
9.
Isabel Echeverria Ping-Chung Su Sindee L. Simon Donald J. Plazek 《Journal of Polymer Science.Polymer Physics》1995,33(17):2457-2468
Creep and differential scanning calorimetry (DSC) measurements have been used to study the physical aging behavior of a polyetherimide. Isothermal aging temperatures ranged from 160°C to Tg with aging times ranging from 10 min to 8 days. The only measurable effect of physical aging on the short-time creep curves is a shift of the creep compliance to longer times. Andrade plots of the compliance versus the cube root of time are linear at short times with the slope β decreasing with increasing aging time to a constant value once equilibrium is reached. Log β3 is related directly to the degree to which the creep curves shift to longer times with physical aging, and is used in this work as a measure of physical aging. A reduced curve of log β3 versus log aging time is obtained for the aging temperatures investigated by appropriate vertical and horizontal shifts. The enthalpy change during aging increases linearly with the logarithm of the aging time, ta, leveling off at equilibrium at values which increase with decreasing aging temperature. Hence, both nonequilibrium and equilibrium temperature shift factors can be calculated from the DSC data. Good agreement is observed between the equilibrium temperature shift factors obtained from the creep and DSC data. The temperature dependence of the nonequilibrium temperature shift factors is found to be an order of magnitude smaller than that of the equilibrium shift factors. The time scales to reach equilibrium for enthalpy and for mechanical measurements are found to be the same within experimental error. © 1995 John Wiley & Sons, Inc. 相似文献
10.
František Toman Ludvík Beneš 《Journal of inclusion phenomena and macrocyclic chemistry》2007,59(3-4):231-236
Differential molar adsorption enthalpies (DMAE) were determined by gas chromatographic measurements of specific retention
volume of vapors on the surface of two forms of Mg–Al hydrotalcite. A linear dependence of the DMAE on the number of the carbon
atoms in hydrocarbons was observed for both form of hydrotalcite. The dependence of the differential molar adsorption enthalpies
on the number of chlorine atoms in organic molecules is discussed. A linear dependence of DMAE on the molecular weight of
chloroderivatives of methane and ethylene on the basic form in an order monochloromethane < dichloromethane < trichloromethane
or vinylidene chloride < 1,1-dichloroethylene < trichloroethylene was found. 相似文献