全文获取类型
收费全文 | 214篇 |
免费 | 39篇 |
国内免费 | 52篇 |
专业分类
化学 | 288篇 |
晶体学 | 2篇 |
综合类 | 3篇 |
物理学 | 12篇 |
出版年
2024年 | 1篇 |
2023年 | 6篇 |
2022年 | 9篇 |
2021年 | 9篇 |
2020年 | 25篇 |
2019年 | 10篇 |
2018年 | 15篇 |
2017年 | 6篇 |
2016年 | 12篇 |
2015年 | 18篇 |
2014年 | 21篇 |
2013年 | 19篇 |
2012年 | 9篇 |
2011年 | 16篇 |
2010年 | 13篇 |
2009年 | 14篇 |
2008年 | 2篇 |
2007年 | 16篇 |
2006年 | 8篇 |
2005年 | 5篇 |
2004年 | 10篇 |
2003年 | 8篇 |
2002年 | 6篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1998年 | 4篇 |
1997年 | 3篇 |
1996年 | 9篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1981年 | 1篇 |
排序方式: 共有305条查询结果,搜索用时 62 毫秒
11.
Pentafluorophenyliodine(III) Compounds. 2. Fluorine-Aryl Substitution Reactions on Iodinetrifluoride: Synthesis of Pentafluorophenyliodinedifluoride C6F5IF2 and Bis(pentafluorophenyl)iodonium Pentafluorophenylfluoroborates[(C6F5)2I]+[(C6F5)nBF4?n]? Mono- and disubstitution can be achieved in the fluorine-aryl substitution reaction on the low-temperature phase IF3 in CH2Cl2 at ?78°C depending on the aryl transfer reagent. With B(C6F5)3 [(C6F5)2I]+ [(C6F5)nBF4?n]? (68% yield) and with Cd(C6F5)2 C6F5IF2 (97% yield) is obtained whereas with C6F5SiMe3 no fluorine-aryl substitution takes place on IF3 even under basic conditions (EtCN or F? addition). At ?78°C in EtCN solution IF3 does not disproportionate but attacks the solvent under formation of HF. 相似文献
12.
In recent years, many optically active β-amino alcohols, mostly derived from naturally occurring α-amino acids, have been incorporated into the asymmetric synthesis as chiral auxiliaries or ligands.1 An effective asymmetric catalysts, the oxazaborolidine-borane reagents, which were originally pioneered by Itsuno and Corey,2 were generally prepared from chiral β-amino alcohols by the reaction with boric acid or formed in situ in the presence of borane. These reagents provide excellent enanti… 相似文献
13.
Preparation and characterization of the first derivatives of the fused macropolyhedral anion [B22H22]2− are reported. The species [B22H21OH]2− (1) and [B22H21OEt]2− (2) are obtained from workup of the products of the reaction between HgBr2 and [NBzlEt3]2[B22H22]; a cluster involving the conjoining of a closo-B12 icosahedron with a nido-B10 cluster. Washing the products with ethanol followed by thin-layer chromatography allows the isolation of 1 and 2, reproducibly, in yields of 27 and 20%, respectively. The species were characterized by NMR spectroscopy, elemental analysis and X-ray diffraction studies. The crystal structure determinations of the two species identify novel features. Apparently the influence of the O atoms in the ions [B22H21OH]2− and [B22H21OEt]2− results in the lengthening of what was a gunwale B---B connection adjacent to the junction of the two cages such that the distances are 2.180 and 2.230 Å, respectively. These latter are longer than the corresponding distance in the parent species [B22H22]2−, which is 2.09 Å; quite long for a normal B---B distance. Thus it is assumed that these B atoms, in 1 and 2, one of which bears the substituent, are not bonded to each other. 相似文献
14.
Kunchala Dhanunjayarao Shreenibasa Sa Basava Punna Rao Aradhyula Krishnan Venkatasubbaiah 《Tetrahedron》2018,74(40):5819-5825
The synthesis of N,C-coordinated organoboron compounds (B1-B4) based on phenanthroimidazole described. All the compounds were characterized by various spectroscopic techniques. Single crystal X-ray diffraction analysis of the compounds B1 and B3 revealed that the vicinity around the boron atom adopts tetrahedral geometry. Except compound B4, other organoboron compounds (B1-B3) does not show solvatochromism. All our newly synthesized organoboron compounds exhibited moderate to good solution state quantum yields (0.07–0.88) and moderate solid state quantum yields. 相似文献
15.
16.
Direct Introduction of a Dimesitylboryl Group Using Base‐Mediated Substitution of Aryl Halides with Silyldimesitylborane
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Eiji Yamamoto Kiyotaka Izumi Ryosuke Shishido Prof. Dr. Tomohiro Seki Noriaki Tokodai Prof. Dr. Hajime Ito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(49):17547-17551
The first dimesitylboryl substitution of aryl halides with a silylborane bearing a dimesitylboryl group in the presence of alkali‐metal alkoxides is described. The reactions of aryl bromides or iodides with Ph2MeSi?BMes2 and Na(OtBu) afforded the desired aryl dimesitylboranes in good to high yields and with high borylation/silylation ratios. Selective reaction of the sterically less‐hindered C?Br bond of dibromoarenes provided monoborylated products. This reaction was used to rapidly construct a D‐π‐A aryl dimesityl borane with a non‐symmetrical biphenyl spacer. 相似文献
17.
18.
Towards the design of novel boron‐ and nitrogen‐substituted ammonia‐borane and bifunctional arene ruthenium catalysts for hydrogen storage
下载免费PDF全文
![点击此处可从《Journal of computational chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Sateesh Bandaru Niall J. English Andrew D. Phillips J.M.D. MacElroy 《Journal of computational chemistry》2014,35(12):891-903
Electronic‐structure density functional theory calculations have been performed to construct the potential energy surface for H2 release from ammonia‐borane, with a novel bifunctional cationic ruthenium catalyst based on the sterically bulky β‐diketiminato ligand (Schreiber et al., ACS Catal. 2012, 2, 2505). The focus is on identifying both a suitable substitution pattern for ammonia‐borane optimized for chemical hydrogen storage and allowing for low‐energy dehydrogenation. The interaction of ammonia‐borane, and related substituted ammonia‐boranes, with a bifunctional η6‐arene ruthenium catalyst and associated variants is investigated for dehydrogenation. Interestingly, in a number of cases, hydride‐proton transfer from the substituted ammonia‐borane to the catalyst undergoes a barrier‐less process in the gas phase, with rapid formation of hydrogenated catalyst in the gas phase. Amongst the catalysts considered, N,N‐difluoro ammonia‐borane and N‐phenyl ammonia‐borane systems resulted in negative activation energy barriers. However, these types of ammonia‐boranes are inherently thermodynamically unstable and undergo barrierless decay in the gas phase. Apart from N,N‐difluoro ammonia‐borane, the interaction between different types of catalyst and ammonia borane was modeled in the solvent phase, revealing free‐energy barriers slightly higher than those in the gas phase. Amongst the various potential candidate Ru‐complexes screened, few are found to differ in terms of efficiency for the dehydrogenation (rate‐limiting) step. To model dehydrogenation more accurately, a selection of explicit protic solvent molecules was considered, with the goal of lowering energy barriers for H‐H recombination. It was found that primary (1°), 2°, and 3° alcohols are the most suitable to enhance reaction rate. © 2014 Wiley Periodicals, Inc. 相似文献
19.
分别以硼氨配合物和硼氢化钠为还原剂合成了核壳结构的Cu@CoW三元合金催化剂和非核壳结构的CuCoW三元合金催化剂,25℃下,Cu0.4@Co0.5W0.1三元合金催化剂对于硼氨配合物水解反应的TOF(转换频率)值达到0.369 0 molH2·molcat-1·s-1,明显高于非核壳结构的Cu0.4Co0.5W0.1催化剂,接近Pt、Pd等贵金属的催化活性,反应的活化能为49 kJ·mol-1。与非核壳结构的CuCoW合金相比,核壳结构的Cu@CoW三元合金催化剂的催化性能及稳定性均有明显提高。 相似文献
20.
合成了蜂窝状的分级多孔碳,并以多孔碳为载体通过浸渍-化学还原法制备碳载镍(Ni/C)作为催化氨硼烷水解制氢的催化剂。采用XRD、BET、SEM、Raman、TEM等手段对样品进行了表征并研究了Ni/C室温催化性能。结果显示,多孔碳比表面积高达737 m2·g-1,具有部分石墨化结构;负载的非晶态镍纳米颗粒平均粒径约为10 nm,均匀分布在碳基材。碳载镍对氨硼烷水解反应具有良好的催化活性,镍负载量为30wt%时催化性能最佳,298 K温度下放氢速率达到1 304.67 mL·min-1·g-1,活化能为29.1 kJ·mol-1,并且具备一定的催化稳定性,表明Ni/C可作为一种廉价高效的催化剂应用于催化氨硼烷水解制氢。 相似文献