首页 | 官方网站   微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   180篇
  免费   2篇
数理化   182篇
  2021年   3篇
  2020年   3篇
  2019年   2篇
  2018年   2篇
  2016年   2篇
  2015年   2篇
  2014年   4篇
  2013年   10篇
  2012年   6篇
  2011年   11篇
  2010年   4篇
  2009年   5篇
  2008年   7篇
  2007年   3篇
  2006年   6篇
  2005年   5篇
  2004年   5篇
  2003年   7篇
  2002年   4篇
  2001年   6篇
  1999年   3篇
  1998年   5篇
  1995年   5篇
  1994年   8篇
  1993年   2篇
  1991年   2篇
  1990年   1篇
  1989年   1篇
  1988年   2篇
  1987年   3篇
  1986年   1篇
  1985年   5篇
  1984年   2篇
  1983年   1篇
  1982年   6篇
  1981年   6篇
  1980年   3篇
  1979年   3篇
  1978年   1篇
  1977年   3篇
  1976年   2篇
  1975年   6篇
  1974年   3篇
  1973年   2篇
  1972年   1篇
  1971年   1篇
  1970年   1篇
  1966年   1篇
  1936年   1篇
  1924年   2篇
排序方式: 共有182条查询结果,搜索用时 15 毫秒
1.
2.
3.
4.
The complexes CoH(PF3)4?n (PPh3)n (n = 1–3) have been prepared by low from the reaction between CoH(PF3)(PPh3)3 and butadiene. The hydrido complexes are active catalysts for the isomerisation of 1-octene to 2-octene under hydrogen or nitrogen.  相似文献   
5.
Rh(π-C3H5)(PF3)3 (I), reacts with trifluoroacetic acid to form propene and [Rh(CF3COO)(PF3)2]2 (II). I reacts with t-butyl bromide to give [RhBr(PF3)2]2 and a mixture of propene and 2-methyl-1-propene and with n-propyl bromide to give propene and [RhBr(PF3)2]2. Rh(π-C3H5)(PPh3)2 (III), and t-butyl bromide yield propene and 2-methyl-1-propene. In these reactions a mechanism involving β-hydrogen abstraction and hydrogen migration via the metal to carbon is proposed. When III reacts with Me3SnCl the Me3Sn—moiety migrates intact to the π-allyl group. I reacts with acetyl chloride to give propene, [RhCl(PF3)2]2 and the carbonyl rhodium complex Rh2Cl2(PF3)3(CO). II does not apparently undergo phosphine ligand exchange unlike the analogous halogeno-bridged dimers.  相似文献   
6.
A new perfluorinated acrylate monomer containing the SF5(CF2)6-perfluorinated side chain was synthesized and polymerized into films. Bulk monomer characterization is consistent with the molecular structure based on FTIR, mass spectrometry and NMR analyses. The surface properties of polymer coatings were studied with aqueous wetting (contact angle) and X-ray photoelectron spectroscopy (XPS) methods. The surface composition is shown to be highly enriched in the terminal side chain SF5-chemistry and exhibits properties consistent with a highly apolar, non-wetting perfluorinated polymer surface. Depth-dependent XPS studies using angular-resolved methods (ADXPS) confirmed a non-stoichiometric enrichment of sulfur and fluorine at the film ambient interface, consistent with a surface presence of the terminal SF5-group and possibly film structural anisotropy in the surface zone. Time-of-flight (TOF) secondary ion mass spectrometry (SIMS) analysis supplements the XPS data by showing the presence of all expected SF5-acrylate chemistry components in the outer 15 Å of the film surface.  相似文献   
7.
Molecular clips derived from 2,4,6,8-tetraazabicyclo[3.3.1]nonane-3,7-dione promote increased regioselectivity in the SO2Cl2-mediated electrophilic aromatic chlorination of ortho-cresol leading to para/ortho ratios (Rp/o) <25; approximately six times larger than in the absence of the clip. Specific recognition events involving hydrogen-bond, π-π and dative covalent interactions are implicated.  相似文献   
8.
9.
Several independent synthetic routes are described leading to the formation of a novel unsaturated tetracyclic phosphorus carbon cage compound tBu4C4P6 (1), which undergoes a light-induced valence isomerization to produce the first hexaphosphapentaprismane cage tBu4C4P6 (2). A second unsaturated isomer tBu4C4P6 (9) of 1 and the bis-[W(CO)5] complex 13 of 1 are stable towards similar isomerization reactions. Another starting material for the synthesis of the hexaphosphapentaprismane cage tBu4C4P6 (2) is the trimeric mercury complex [(tBu4C4P6)Hg]3 (11), which undergoes elimination of mercury to afford the title compound 2. Single-crystal X-ray structural determinations have been carried out on compounds 1, 2, 9, 11, and 13.  相似文献   
10.
Results of a study of the valence electronic structure of norbornene (C(7)H(10)), up to binding energies of 30 eV, are reported. Experimental electron momentum spectroscopy (EMS) and theoretical Green's function and density functional theory approaches were utilized in this investigation. A stringent comparison between the electron momentum spectroscopy and theoretical orbital momentum distributions found that, among the tested models, the combination of the Becke-Perdew functional and a polarized valence basis set of triple-zeta quality provides the best representation of the electron momentum distributions for all 19 valence orbitals of norbornene. This experimentally validated model was then used to extract other molecular properties of norbornene (geometry, infrared spectrum). When these calculated properties are compared to corresponding results from independent measurements, reasonable agreement is typically found. Due to the improved energy resolution, EMS is now at a stage to very finely image the effective topology of molecular orbitals at varying distances from the molecular center, and the way the individual atomic components interact with each other, often in excellent agreement with theory. This will be demonstrated here. Green's Function calculations employing the third-order algebraic diagrammatic construction scheme indicate that the orbital picture of ionization breaks down at binding energies larger than about 22 eV. Despite this complication, they enable insights within 0.2 eV accuracy into the available ultraviolet emission and newly presented (e,2e) ionization spectra. Finally, limitations inherent to calculations of momentum distributions based on Kohn-Sham orbitals and employing the vertical depiction of ionization processes are emphasized, in a formal discussion of EMS cross sections employing Dyson orbitals.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司    京ICP备09084417号-23

京公网安备 11010802026262号