全文获取类型
收费全文 | 93篇 |
免费 | 0篇 |
专业分类
化学 | 53篇 |
数学 | 4篇 |
物理学 | 36篇 |
出版年
2019年 | 1篇 |
2017年 | 1篇 |
2014年 | 3篇 |
2013年 | 4篇 |
2012年 | 1篇 |
2011年 | 1篇 |
2010年 | 1篇 |
2008年 | 6篇 |
2007年 | 3篇 |
2006年 | 7篇 |
2005年 | 7篇 |
2004年 | 1篇 |
2003年 | 1篇 |
2002年 | 3篇 |
2001年 | 2篇 |
2000年 | 5篇 |
1999年 | 2篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 5篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1985年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 3篇 |
1969年 | 3篇 |
1968年 | 2篇 |
1943年 | 2篇 |
1924年 | 1篇 |
1908年 | 2篇 |
1886年 | 2篇 |
排序方式: 共有93条查询结果,搜索用时 15 毫秒
1.
2.
The rate of reductive elimination for a family of zirconocene isobutyl hydride complexes, Cp(CpR(n)())Zr(CH(2)CHMe(2))H (Cp = eta(5)-C(5)Me(5), CpR(n)() = substituted cyclopentadienyl), has been measured as a function of cyclopentadienyl substituent. In general, the rate of reductive elimination increases modestly with the incorporation of sterically demanding substituents such as [CMe(3)] or [SiMe(3)]. A series of isotopic labeling experiments was used to elucidate the mechanism and rate-determining step for the reductive elimination process. From these studies, a new zirconocene isobutyl hydride complex, Cp' '(2)Zr(CH(2)CHMe(2))(H) (Cp' ' = eta(5)-C(5)H(3)-1,3-(SiMe(3))(2)), was designed and synthesized such that facile reductive elimination of isobutane and activation of dinitrogen was observed. The resulting dinitrogen complex, [Cp' '(2)Zr](2)(mu(2), eta(2),eta(2)-N(2)), has been characterized by X-ray diffraction and displays a bond length of 1.47 A for the N(2) ligand, the longest observed in any metallocene dinitrogen complex. Solution magnetic susceptibility demonstrates that [Cp' '(2)Zr](2)(mu(2), eta(2), eta(2)-N(2)) is a ground-state triplet, consistent with two Zr(III), d(1) centers. Mechanistic studies reveal that the dinitrogen complex is derived from the reaction of N(2) with the resulting cyclometalated zirconocene hydride rather than directly from reductive elimination of alkane. 相似文献
3.
Steven J. P’Pool 《Journal of organometallic chemistry》2005,690(15):3522-3528
Oxidative addition of methyl iodide to Vaska’s complex in the ionic liquids 1-butyl-3-methylimidazolium triflate [C4mim][OTf], [C4mim] bis(trifluormethylsulfonyl)imide [Tf2N], and N-hexylpyridinium [C6pyr][Tf2N] occurred cleanly to give the expected Ir(III) oxidative addition product. Pseudo-first order rate constants were determined for the oxidative addition reaction in each solvent ([Vaska’s] = 0.25 mM, [CH3I] = 37.5 mM). The observed rate constants under these conditions were 5-10 times slower than the rate seen in DMF. At high methyl iodide concentrations (>23 mM), the expected first order dependence on methyl iodide was not observed. In each ionic liquid, there was no change in the reaction rates within experimental error over the methyl iodide concentration range of 23-75 mM. At lower methyl iodide concentration, a decrease in rate was observed in [C4mim][Tf2N] with decreasing concentration of methyl iodide. 相似文献
4.
5.
An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol?1)·T?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH3 group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition. 相似文献
6.
Abstract Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood. 相似文献
7.
8.
We determine the free energy of micelle formation for model surfactants in a Lennard-Jones solvent by employing a hybrid semi-grand Monte Carlo simulation scheme in combination with umbrella sampling and configurational bias techniques. Comparing the results to theoretical prediction, we obtain good agreement for large micellar sizes. We also study the effect of changing the surfactant headgroup size and tail length on the critical micelle concentration. The values of and the trends in the calculated critical micelle concentrations do agree with experimental observation for nonionic surfactants. The results open up the way for the calculation of critical micelle concentrations using realistic atomic force fields. 相似文献
9.
The stability of colloidal dispersions can be severely affected by the presence of surfactants. Because surfactants can adsorb at colloidal surfaces as well as form micelles, one can expect an interplay between both phenomena. Using grand-canonical coarse-grained Monte Carlo simulations on surfactant solutions confined between two surfaces, we investigate how adsorption and micelle formation affects the effective interaction between two colloidal particles, and hence, the stability of the colloidal dispersion. For solvophilic colloidal surfaces, we observe a short-ranged oscillatory solvation pressure that is hardly affected by the presence of surfactants in the system. The effective surface-surface interaction, however, reveals a decrease in solvophilic stabilization as a function of surfactant chemical potential. For solvophobic surfaces, we find that the capillary evaporation observed in a confined pure solvent, is counteracted by the addition of surfactants. Around the critical micelle concentration (CMC), the surface-surface interaction even becomes repulsive, enhancing stabilization of the colloidal dispersion. In contrast, the formation of micelles at concentrations above the CMC causes an additional depletion effect, resulting in an effective attraction, which in turn can destabilize a colloidal dispersion. 相似文献
10.