首页 | 本学科首页   官方微博 | 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   371篇
  免费   26篇
  国内免费   1篇
化学   288篇
力学   5篇
数学   16篇
物理学   89篇
  2023年   4篇
  2022年   8篇
  2021年   6篇
  2020年   8篇
  2019年   8篇
  2017年   7篇
  2016年   25篇
  2015年   10篇
  2014年   4篇
  2013年   16篇
  2012年   21篇
  2011年   11篇
  2010年   8篇
  2009年   8篇
  2008年   13篇
  2007年   16篇
  2006年   23篇
  2005年   13篇
  2004年   13篇
  2003年   17篇
  2002年   11篇
  2001年   10篇
  2000年   6篇
  1999年   7篇
  1997年   5篇
  1995年   3篇
  1994年   7篇
  1993年   6篇
  1991年   4篇
  1990年   7篇
  1989年   5篇
  1986年   8篇
  1985年   5篇
  1984年   4篇
  1983年   5篇
  1982年   5篇
  1981年   4篇
  1980年   5篇
  1977年   3篇
  1972年   2篇
  1970年   2篇
  1969年   2篇
  1968年   2篇
  1967年   5篇
  1966年   3篇
  1965年   4篇
  1963年   2篇
  1962年   4篇
  1961年   4篇
  1959年   2篇
排序方式: 共有398条查询结果,搜索用时 15 毫秒
311.
312.
Poly(triazine imide) with incorporated lithium chloride has recently attracted substantial attention due to its photocatalytic activity for water splitting. However, an apparent H/Li disorder prevents the delineation of structure–property relationships, for example, with respect to band‐gap tuning. Herein, we show that through a combination of one‐ and two‐dimensional, multinuclear solid‐state NMR spectroscopy, chemical modelling, automated electron diffraction tomography, and an analysis based on X‐ray pair distribution functions, it is finally possible to resolve the H/Li substructure. In each cavity, one hydrogen atom is bound to a bridging nitrogen atom, while a second one protonates a triazine ring. The two lithium ions within each cavity are positioned between two nitrogen atoms of neighbouring triazine rings. The thereby induced local dipole moments cause slight buckling of the framework and lateral displacements of the Cl? ions at a coherence length below 2 nm. Nevertheless, the average structure conforms to space group P212121. In this way, we demonstrate that, in particular, the above‐mentioned techniques allow for smart interplay in delineating the real structure of PTI/LiCl.  相似文献   
313.
314.
315.
A rapid and productive vicinal diamination of alkenes takes place in the presence of a hypervalent iodine(III) reagent and bissulfonimides as nitrogen sources. A total of more than 60 examples are presented. The reaction is characterized by its robustness and its wide substrate scope: it proceeds selectively with both terminal and internal alkenes and tolerates a range of functional groups.  相似文献   
316.
New palladium(II)–phthalimidato complexes have been synthesized, isolated, and structurally characterized. As demonstrated from over 30 examples, they constitute superior catalysts for oxidative amination reactions of alkenes with phthalimide as the nitrogen source. This work streamlines vicinal difunctionalization of alkenes and provides access to significantly improved and experimentally simplified synthetic protocols.  相似文献   
317.
A series of benzyl(diphenylphosphino) and o‐phenyl(diphenlyphosphino) substituted germylenes and plumbylenes were synthesized by nucleophilic substitution between the respective lithium reagent and tetrylene halide. The Lewis pairs were characterized by X‐ray crystallography and NMR spectroscopy. The reactivity of the tetrylenes was investigated with respect to azide addition. In the germylene case, the germaniumimide was formed as the kinetically controlled product, which rearranges upon heating to give the phosphinimide. The stannylene and plumbylene derivatives react with adamantylazide to give the azide adducts. 1‐Pentene reacts diastereoselectively with the phosphagermirane to give a cyclic addition product. Trimethysilylacetylene shows an addition with the benzylphosphino‐substituted germylene and plumbylene to give the cycloheteropentene molecules. The addition product between phenylacetylene and the four membered Ge‐P adduct shows after addition at room temperature a 1,4‐phenylmigration to give a cyclic phosphine. Alkylnitrene insertion into a Ge?C bond of the alkyne addition product of the phosphagermirane was found in reaction with adamantylazide.  相似文献   
318.
A computational study of the mechanism for the iodine(III)‐mediated oxidative amination of alkenes explains the experimentally observed substrate dependence on product distribution. Calculations with the M06 functional have been carried out on the reaction between PhI(N(SO2Me)2)2 and three different representative substrates: styrene, α‐methylstyrene, and (E)‐methylstilbene. All reactions start with electrophilic attack by a cationic PhI(N(SO2Me)2)+ unit on the double bond, and formation of an intermediate with a single C?I bond and a planar sp2 carbocationic center. The major path, leading to 1,2‐diamination, proceeds through a mechanism in which the bissulfonimide initially adds to the alkene through an oxygen atom of one sulfonyl group. This behavior is now corroborated by experimental evidence. An alternative path, leading to an allylic amination product, takes place through deprotonation at an allylic C?H position in the common intermediate. The regioselectivity of this amination depends on the availability of the resonant structures of an alternate carbocationic intermediate. Only in cases where a high electronic delocalization is possible, as in (E)‐methylstilbene, does the allylic amination occur without migration of the double bond.  相似文献   
319.
320.
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