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   783篇
  免费   36篇
化学   648篇
晶体学   4篇
力学   17篇
数学   69篇
物理学   81篇
  2024年   1篇
  2023年   8篇
  2022年   13篇
  2021年   51篇
  2020年   32篇
  2019年   59篇
  2018年   37篇
  2017年   35篇
  2016年   37篇
  2015年   37篇
  2014年   24篇
  2013年   55篇
  2012年   61篇
  2011年   56篇
  2010年   47篇
  2009年   30篇
  2008年   51篇
  2007年   31篇
  2006年   37篇
  2005年   33篇
  2004年   13篇
  2003年   20篇
  2002年   11篇
  2001年   8篇
  2000年   4篇
  1999年   5篇
  1998年   4篇
  1997年   3篇
  1996年   2篇
  1995年   1篇
  1994年   2篇
  1993年   1篇
  1991年   1篇
  1990年   2篇
  1989年   1篇
  1981年   1篇
  1975年   1篇
  1974年   2篇
  1972年   2篇
排序方式: 共有819条查询结果,搜索用时 31 毫秒
31.
32.
N-Heterocyclic carbene (NHC) ligands are ubiquitously utilized in catalysis. A common catalyst design model assumes strong M–NHC binding in this metal–ligand framework. In contrast to this common assumption, we demonstrate here that lability and controlled cleavage of the M−NHC bond (rather than its stabilization) could be more important for high-performance catalysis at low catalyst concentrations. The present study reveals a dynamic stabilization mechanism with labile metal–NHC binding and [PdX3][NHC-R]+ ion pair formation. Access to reactive anionic palladium intermediates formed by dissociation of the NHC ligands and plausible stabilization of the molecular catalyst in solution by interaction with the [NHC-R]+ azolium ion is of particular importance for an efficient and recyclable catalyst. These ionic Pd/NHC complexes allowed for the first time the recycling of the complex in a well-defined form with isolation at each cycle. Computational investigation of the reaction mechanism confirms a facile formation of NHC-free anionic Pd in polar media through either Ph–NHC coupling or reversible H–NHC coupling. The present study formulates novel ideas for M/NHC catalyst design.  相似文献   
33.
34.
Chemistry of Heterocyclic Compounds - 4-Acyl-2-amino-6-chloropyridine-3,5-dicarbonitriles underwent heterocyclization in the presence of ammonia in aqueous dioxane medium, involving the...  相似文献   
35.
36.
Pincer complexes featuring readily tunable tridentate ligand frameworks comprise one of the most actively studied classes of organometallic and metal–organic compounds and find extensive use in catalysis, organic synthesis, materials science, and other fields of chemistry and allied disciplines. Currently growing attention is devoted to non‐classical ligand scaffolds, such as functionalized carboxamides, which offer multiple options for directed structural modifications. In this study, the reactions of (methylsulfanyl)acetyl and propanoyl chlorides with 2‐(aminomethyl)pyridine, 2‐(2‐aminoethyl)pyridine, 8‐aminoquinoline and 2‐(diphenylthiophosphoryl)aniline afford a series of new pincer‐type ligands based on functionalized carboxamides. The ligands obtained readily undergo direct cyclopalladation under the action of PdCl2(NCPh)2 in dichloromethane at room temperature, resulting in Pd(II) pincer complexes with N,N,S‐ and S,N,S‐donor sets. Importantly, some of the cyclopalladated derivatives can also be produced efficiently under solvent‐free conditions according to the approach recently developed by our group. The complexes obtained have been tested for cytotoxicity against several human cancer cell lines and catalytic activity in the model Suzuki reaction. The results have been compared to those for the related Pd(II) pincer complexes to define the main structure–activity relationships and to outline the most promising structures for further investigations.  相似文献   
37.
This study presents the synthesis of organoboron derivatives of stereoregular 4-, 6-, and 12-unit phenylcyclosilsesquioxanes. All compounds obtained were isolated in good yields (70–80 %) and were fully characterized by 1H, 13C, 29Si, 11B NMR, IR spectroscopy, HRMS ESI, and elemental microanalysis. The structure of the key modifier, obtained for the first time, 4-(tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl) dimethylvinylsilane, was also confirmed by single-crystal XRD.  相似文献   
38.
39.
Novel types of hydrazinopeptide-like units containing five elements of diversity have been prepared in two steps using sequential Ugi reactions.  相似文献   
40.
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