全文获取类型
收费全文 | 645篇 |
免费 | 53篇 |
专业分类
化学 | 604篇 |
力学 | 1篇 |
数学 | 56篇 |
物理学 | 37篇 |
出版年
2023年 | 4篇 |
2022年 | 5篇 |
2021年 | 14篇 |
2020年 | 17篇 |
2019年 | 18篇 |
2018年 | 4篇 |
2017年 | 2篇 |
2016年 | 31篇 |
2015年 | 19篇 |
2014年 | 27篇 |
2013年 | 32篇 |
2012年 | 39篇 |
2011年 | 71篇 |
2010年 | 26篇 |
2009年 | 29篇 |
2008年 | 43篇 |
2007年 | 48篇 |
2006年 | 51篇 |
2005年 | 46篇 |
2004年 | 29篇 |
2003年 | 18篇 |
2002年 | 27篇 |
2001年 | 7篇 |
2000年 | 7篇 |
1999年 | 4篇 |
1998年 | 3篇 |
1997年 | 7篇 |
1996年 | 14篇 |
1995年 | 6篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 7篇 |
1991年 | 4篇 |
1990年 | 7篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1960年 | 1篇 |
1891年 | 1篇 |
排序方式: 共有698条查询结果,搜索用时 218 毫秒
41.
42.
43.
The optimization of P,S-ligands derived from enantiopure (2S,3S)-phenylglycidol for asymmetric rhodium-catalyzed hydrogenation of dehydroamino esters is described. The exceptionally high modular character of the (2S,3S)-phenylglycidol platform is demonstrated by systematic modification of the ether and thioether moieties, the skeletal aryl substituent and the stereo and regiochemistry of the ligands. An experimentally useful method for the monitoring of hydrogenation reactions is also described and used for obtaining relevant data of the catalytic systems studied. 相似文献
44.
45.
Dr. Carmen E. Castillo Dr. Ilaria Gamba Laia Vicens Dr. Martin Clémancey Prof. Dr. Jean-Marc Latour Prof. Dr. Miquel Costas Prof. Dr. Manuel G. Basallote 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(15):4946-4954
Oxoiron(IV) complexes bearing tetradentate ligands have been extensively studied as models for the active oxidants in non-heme iron-dependent enzymes. These species are commonly generated by oxidation of their ferrous precursors. The mechanisms of these reactions have seldom been investigated. In this work, the reaction kinetics of complexes [FeII(CH3CN)2L](SbF6)2 ( [1](SbF6)2 and [2](SbF6)2 ) and [FeII(CF3SO3)2L] ( [1](OTf)2 and [2](OTf)2 ( 1 , L=Me,HPytacn; 2 , L=nP,HPytacn; R,R′Pytacn=1-[(6-R′-2-pyridyl)methyl]-4,7- di-R-1,4,7-triazacyclononane) with Bu4NIO4 to form the corresponding [FeIV(O)(CH3CN)L]2+ ( 3 , L=Me,HPytacn; 4 , L=nP,HPytacn) species was studied in acetonitrile/acetone at low temperatures. The reactions occur in a single kinetic step with activation parameters independent of the nature of the anion and similar to those obtained for the substitution reaction with Cl− as entering ligand, which indicates that formation of [FeIV(O)(CH3CN)L]2+ is kinetically controlled by substitution in the starting complex to form [FeII(IO4)(CH3CN)L]+ intermediates that are converted rapidly to oxo complexes 3 and 4 . The kinetics of the reaction is strongly dependent on the spin state of the starting complex. A detailed analysis of the magnetic susceptibility and kinetic data for the triflate complexes reveals that the experimental values of the activation parameters for both complexes are the result of partial compensation of the contributions from the thermodynamic parameters for the spin-crossover equilibrium and the activation parameters for substitution. The observation of these opposite and compensating effects by modifying the steric hindrance at the ligand illustrates so far unconsidered factors governing the mechanism of oxygen atom transfer leading to high-valent iron oxo species. 相似文献
46.
47.
[reaction: see text] An unprecedented endo-selective and regioselective intermolecular Pauson-Khand reaction takes place when heterobimetallic (Mo-Co) complexes derived from N-(2-alkynoyl)oxazolidinones or sultams are heated in the presence of norbornadiene. 相似文献
48.
49.
The energy barriers for the addition to ethylene of a series of carbenes have been calculated at an ab initio level. using the STO-3G and 3-21G basis sets. It is shown that the usual extrapolation of experiment results, which predicts that the reactivity of carbenes decreases when increasing its nucleophilic character, is not valid. 相似文献
50.