全文获取类型
收费全文 | 156篇 |
免费 | 15篇 |
专业分类
化学 | 167篇 |
物理学 | 4篇 |
出版年
2023年 | 3篇 |
2022年 | 1篇 |
2021年 | 3篇 |
2020年 | 4篇 |
2019年 | 5篇 |
2018年 | 3篇 |
2017年 | 3篇 |
2016年 | 2篇 |
2015年 | 8篇 |
2014年 | 5篇 |
2013年 | 5篇 |
2012年 | 9篇 |
2011年 | 16篇 |
2010年 | 1篇 |
2009年 | 2篇 |
2008年 | 10篇 |
2007年 | 6篇 |
2006年 | 8篇 |
2005年 | 11篇 |
2004年 | 6篇 |
2003年 | 4篇 |
2002年 | 3篇 |
2001年 | 7篇 |
1996年 | 4篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1991年 | 3篇 |
1989年 | 2篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1979年 | 1篇 |
1977年 | 6篇 |
1976年 | 2篇 |
1975年 | 4篇 |
1974年 | 1篇 |
1973年 | 4篇 |
1971年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有171条查询结果,搜索用时 15 毫秒
11.
Dr. Ryu Yamasaki Dr. Masato Ohashi Kyotaro Maeda Takuya Kitamura Minami Nakagawa Korehito Kato Tetsushi Fujita Ryohei Kamura Kazuto Kinoshita Dr. Hyuma Masu Prof. Dr. Isao Azumaya Prof. Dr. Sensuke Ogoshi Prof. Dr. Shinichi Saito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(10):3415-3425
A detailed study of the Ni‐catalyzed [4+3+2] cycloaddition reaction between ethyl cyclopropylideneacetate and dienynes has been conducted, resulting in the development of a new method for the synthesis of compounds containing nine‐membered rings. We studied the reactivity of various dienynes, together with their substituent and conformational effects. The mechanism of the reaction was probed by examining the stoichiometric reactions of the Ni complexes and dienynes. 相似文献
12.
Dr. Masato Ohashi Ryohei Doi Prof. Dr. Sensuke Ogoshi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(7):2040-2048
This report describes the first Pd0‐catalyzed cross‐coupling of hexafluorobenzene (C6F6) with diarylzinc compounds to give a variety of pentafluorophenyl arenes. This reaction could be applied to other perfluoroarenes, such as octafluorotoluene, pentafluoropyridine, and perfluoronaphthalene, to give the corresponding polyfluorinated coupling products. The optimal ligand in this catalytic reaction was PCy3, and lithium iodide was indispensable as an additive for the coupling reaction. One of the roles of lithium iodide in this catalytic reaction was to promote the oxidative addition of one C?F bond of C6F6 to palladium. Stoichiometric reactions revealed that an expected oxidative‐addition product, trans‐[Pd(C6F5)I(PCy3)2], generated from the reaction of [Pd(PCy3)2] with C6F6 in the presence of lithium iodide, was not involved in the catalytic cycle. Instead, a transient three‐coordinate, monophosphine‐ligated species, [Pd(C6F5)I(PCy3)], emerged as a potential intermediate in the catalytic cycle. Therefore, we isolated a novel PdII complex, [Pd(C6F5)I(PCy3)(py)], in which pyridine (py) acted as a labile ligand to generate the transient species. In fact, in the presence of lithium iodide, this PdII complex was found to react smoothly with diphenylzinc to give the desired pentafluorophenyl benzene, whereas the same reaction conducted in the absence of lithium iodide resulted in a decreased yield of pentafluorophenyl benzene, which indicated that the other role of lithium iodide was to enhance the reactivity of the organozinc species during the transmetalation step. 相似文献
13.
14.
15.
Kanyiva KS Kashihara N Nakao Y Hiyama T Ohashi M Ogoshi S 《Dalton transactions (Cambridge, England : 2003)》2010,39(43):10483-10494
A combination of Ni(cod)(2) and PCyp(3) is found to be an effective catalyst for chemoselective activation of the C-H bond of fluoroarenes over C-F bonds followed by insertion of alkynes to allow direct alkenylation of the electron-deficient arenes. The characteristics of the reactions are: a C-H bond ortho to a fluorine substituent is selectively activated; the reactivity of fluorobenzenes is roughly proportional to the number of fluorine atoms. The reaction conditions tolerate a broad range of both alkynes and fluoroarenes containing both electron-withdrawing and -donating groups, thus allowing efficient synthesis of a variety of substituted ethenes containing a fluoroaryl motif in high regio- and stereoselective manners. Mechanistic studies including both labeling experiments and stoichiometric reactions reveal that oxidative addition of C-H bonds in fluoroarenes to nickel(0) is kinetically highly facile whereas that of C-F bonds is thermodynamically favoured. 相似文献
16.
Hironori Ohashi Hiroyuki Ezoe Yoshihiro Okaue Yasuhiro Kobayashi Shuji Matsuo Tsutomu Kurisaki Akane Miyazaki Hisanobu Wakita Takushi Yokoyama 《Analytical sciences》2005,21(7):789-793
The effect of UV (ultraviolet) irradiation on the adsorption of Au(III) ions on manganese dioxide and their reduction to Au(0) (gold with 0 valence state) was investigated using XPS (X-ray photoelectron spectroscopy) and 197Au M?ssbauer spectroscopy. The UV irradiation accelerated the adsorption and the reduction. From the fact that the proportion of Au(0) estimated from Au 4f XPS spectra for surface analysis was significantly smaller than that from 197Au M?ssbauer spectra for bulk analysis, we deduced that Au(0) was interpenetrated to the inside of manganese dioxide (into deeper places than about 30 A) where XPS is impossible to detect. The content of surface hydroxyl groups on manganese dioxide also increased due to the UV irradiation. The relationship between the charge in the content of hydroxyl groups and the interpenetration of Au(0) is discussed. 相似文献
17.
Shuichi Ban Yoshiki Takano Naoki Ohkubo Hisanobu Hoya Yumiko Takahashi Kouichi Takase Kazuko Sekizawa 《Hyperfine Interactions》2005,165(1-4):95-99
The transition metal phosphorus trichalcogenides MnPS3 and the FePS3 are CdCl2 type layered compounds, where the transition metal ions form a hexagonal lattice. While these compounds order anti-ferromagnetically at low temperature, the magnetic structures are different. We have reported that these mixtures Mn0.5Fe0.5PS3 is a spin glass with a glass transition temperature T g=33.7 K. Then, in this work, we report that the results of the temperature variation of the 57Fe Mössbauer spectra of FePS3 and Mn0.5Fe0.5PS3, in detail. In the anti-ferromagnetic state of FePS3, the hyperfine magnetic field H int increases with decreasing temperature and the Isomer shift I. S. increases slightly with decreasing temperature. However in Mn0.5Fe0.5PS3, the two broadened peaks are observed and the two peaks became a single peak with decreasing temperature at about 50.0 K, which is higher than T g=33.7 K. In the spin glass Mn0.5Fe0.5PS3, the Mössbauer spectra suggest that the magnetic interactions exist far above T g. 相似文献
18.
Dr. Tomoki Ogoshi Ryuta Sueto Kumiko Yoshikoshi Dr. Yoko Sakata Prof. Shigehisa Akine Prof. Tada‐aki Yamagishi 《Angewandte Chemie (International ed. in English)》2015,54(34):9849-9852
Activated perethylated pillar[5]arene crystals show an unexpected alkane‐shape‐ and ‐length‐selective gate‐opening behavior. Activated crystals were obtained upon removing solvents from perethylated pillar[5]arene crystals by heating. The activated crystals could quantitatively take up n‐alkanes with carbon chains containing more than five carbon atoms as a consequence of their gate‐opening pressure. As the chain length of the n‐alkanes increased, the gate pressure decreased. A transformation into a herringbone structure was induced when n‐hexane was used as a guest. By contrast, cyclic and branched alkanes were not taken up and could not induce a crystal transformation because they were too large to fit in the cavities of the pillar[5]arene. Alkane‐shape‐selective molecular recognition of pillar[5]arenes in the solution state was translated into the vapor/crystal state. 相似文献
19.
A Strategy to Control the Reactivation of Frustrated Lewis Pairs from Shelf‐Stable Carbene Borane Complexes
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Yoichi Hoshimoto Takuya Kinoshita Prof. Dr. Masato Ohashi Prof. Dr. Sensuke Ogoshi 《Angewandte Chemie (International ed. in English)》2015,54(40):11666-11671
N‐Phosphine oxide substituted imidazolylidenes (PoxIms) have been synthesized and fully characterized. These species can undergo significant changes to the spatial environment surrounding their carbene center through rotation of the phosphine oxide moiety. Either classical Lewis adducts (CLAs) or frustrated Lewis pairs (FLPs) are thus formed with B(C6F5)3 depending on the orientation of the phosphine oxide group. A strategy to reactivate FLPs from CLAs by exploiting molecular motions that are responsive to external stimuli has therefore been developed. The reactivation conditions were successfully controlled by tuning the strain in the PoxIm–B(C6F5)3 complexes so that reactivation only occurred above ambient temperature. 相似文献
20.
Photoswitching of the transformation between seconds and hours time-scales is demonstrated using the threading of per-hydroxylated pillar[5]arene onto the azobenzene-end of a viologen derivative. When the azobenzene moiety was in the trans form, the threading of per-hydroxylated pillar[5]arene quickly took place at 25 °C and could not be monitored directly. The exchange rate (k) and half-life time (t(1/2)) examined by 2D EXSY NMR spectroscopy were found to be 0.209 ± 0.013 s(-1) and 3.33 ± 0.21 s, respectively. In contrast, the cis form of the azobenzene moiety required very long time (k = 2.14 ± 0.27 × 10(-5) s(-1), t(1/2) = 9.13 ± 1.2 h) to thread per-hydroxylated pillar[5]arene at 25 °C. Photoisomerization from the trans to the cis form generated the following increment of free energy of activation at 25 °C: ΔG(in)(?) (cis form) - ΔG(in)(?) (trans form) = 22.8 ± 0.24 kJ mol(-1), which led to the time-scale transformation. The tuning of the threading was also accomplished by heating/cooling: the rate constants increased on heating and decreased on cooling. 相似文献