全文获取类型
收费全文 | 246篇 |
免费 | 15篇 |
国内免费 | 6篇 |
专业分类
化学 | 145篇 |
晶体学 | 1篇 |
力学 | 7篇 |
数学 | 65篇 |
物理学 | 49篇 |
出版年
2024年 | 1篇 |
2023年 | 1篇 |
2022年 | 5篇 |
2021年 | 4篇 |
2020年 | 3篇 |
2019年 | 6篇 |
2018年 | 1篇 |
2017年 | 1篇 |
2016年 | 1篇 |
2015年 | 1篇 |
2014年 | 8篇 |
2013年 | 20篇 |
2012年 | 14篇 |
2011年 | 17篇 |
2010年 | 17篇 |
2009年 | 10篇 |
2008年 | 19篇 |
2007年 | 16篇 |
2006年 | 10篇 |
2005年 | 13篇 |
2004年 | 12篇 |
2003年 | 10篇 |
2002年 | 14篇 |
2001年 | 2篇 |
2000年 | 3篇 |
1999年 | 9篇 |
1998年 | 5篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 2篇 |
1994年 | 4篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 4篇 |
1989年 | 3篇 |
1988年 | 1篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1968年 | 2篇 |
排序方式: 共有267条查询结果,搜索用时 46 毫秒
11.
A new general synthesis of substituted coumarins is described. The in situ cycloaddition of chloroketenes with α-methoxymethylenecyclohexanones yields (4 + 2) cycloaddition products, 3,4-dihydro-2-pyranones. The chlorine atom is reductively removed and methanol is spontaneously eliminated to yield the 5,6,7,8-tetra-hydrocoumarins. Dehydrogenation of these compounds results in good yields of the substituted coumarins. 相似文献
12.
Shieh M Cherng JJ Lai YW Ueng CH Peng SM Liu YH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(19):4522-4527
We have discovered a series of novel pentacarbonylchromium derivatives of bismuth from the reactions of NaBiO(3) with [Cr(CO)(6)] in KOH/MeOH solutions. When the reaction was carried out at room temperature, the highly charged [Bi[Cr(CO)(5)](4)](3-) (1) was obtained, whose structure was shown by X-ray analysis to possess a central bismuth atom tetrahedrally coordinated to four [Cr(CO)(5)] groups. As the reaction was heated at 80 degrees C, the methyl-substituted complex [MeBi[Cr(CO)(5)](3)](2-)(2) was obtained, presumably via the CbondO activation of MeOH. Further reactions of 1 with CH(2)Cl(2) or CHtbondCCH(2)Br form the halo-substituted complexes [XBi[Cr(CO)(5)](3)](2-)(X=Cl, 3; Br, 4), respectively. On the other hand, the reactions of 1 with RI (R=Me, Et) led to the formation of the alkyl-substituted complexes [RBi[Cr(CO)(5)](3)](2-)(R=Me, 2; Et). The formation of complexes 1-4 is discussed, presumably via the intermediate bismuthinidene [Bi[Cr(CO)(5)](3)](-) or the trianion [Bi[Cr(CO)(5)](3)](3-). 相似文献
13.
We have synthesized a new series of chromium-group 15 dihydride and hydride complexes [H(2)As(Cr(CO)(5))(2)](-) (1) and [HE(Cr(CO)(5))(3)](2)(-) (E = As, 2a; E = Sb, 2b), which represent the first examples of group 6 complexes containing E-H fragments. The contrasting chemical reactivity of 2a and 2b with organic halogen derivatives is demonstrated. The reaction of 2a with RBr (R = PhCH(2), HC triple bond CCH(2)) produces the RX addition products [(R)(Br)As(Cr(CO)(5))(2)](-) (R = PhCH(2), 3; R = C(3)H(3), 4), while the treatment of 2b with RX (RX = PhCH(2)Br or HC triple bond CCH(2)Br, CH(3)(CH(2))(5)C(O)Cl) forms the halo-substituted complexes [XSb(Cr(CO)(5))(3)](2-) (X = Br, 5; X = Cl, 6). Moreover, the dihaloantimony complexes [XX'Sb(Cr(CO)(5))(2)](-) can be obtained from the reaction of 2b with the appropriate organic halides. In this study, a series of organoarsenic and antimony chromium carbonyl complexes have been synthesized and structurally characterized and the role of the main group on the formation of the resultant complexes is also discussed. 相似文献
14.
15.
Prof. Dr. Minghuey Shieh Chun‐Hsien Yu Yen‐Yi Chu Yu‐Wen Guo Chung‐Yi Huang Kai‐Jieah Hsing Pei‐Chi Chen Chung‐Feng Lee 《化学:亚洲杂志》2013,8(5):963-973
The reactions of E powder (E=S, Se) with a mixture of Cr(CO)6 and Mn2(CO)10 in concentrated solutions of KOH/MeOH produced two new mixed Cr? Mn? carbonyl clusters, [E2CrMn2(CO)9]2? (E=S, 1 ; Se, 2 ). Clusters 1 and 2 were isostructural with one another and each displayed a trigonal‐bipyramidal structure, with the CrMn2 triangle axially capped by two μ3‐E atoms. The analogous telluride cluster, [Te2CrMn2(CO)9]2? ( 3 ), was obtained from the ring‐closure of Te2Mn2 ring complex [Te2Mn2Cr2(CO)18]2? ( 4 ). Upon bubbling with CO, clusters 2 and 3 were readily converted into square‐pyramidal clusters, [E2CrMn2(CO)10]2? (E=Se, 5 ; Te, 6 ), accompanied with the cleavage of one Cr? Mn bond. According to SQUID analysis, cluster 6 was paramagnetic, with S=1 at room temperature; however, the Se analogue ( 5 ) was spectroscopically proposed to be diamagnetic, as verified by TD‐DFT calculations. Cluster 6 could be further carbonylated, with cleavage of the Mn? Mn bond to produce a new arachno‐cluster, [Te2CrMn2(CO)11]2? ( 7 ). The formation and structural isomers, as well as electrochemistry and UV/Vis absorption, of these clusters were also elucidated by DFT calculations. 相似文献
16.
3, 4′-Bipyridine was synthesized from 6-methoxy-3, 4′-bipyridine or 6-benzyloxy-3, 4′-bipyridine via 6-chloro-3, 4′-bipyridine. The chloro derivative was catalytically dechlorinated into the corresponding 3, 4′ -bipyridine. 相似文献
17.
Spencer Knapp Andrew B. J. Naughton Paivi J. Kukkola Wen-Chung Shieh 《Journal of carbohydrate chemistry》2013,32(6):981-993
ABSTRACT For five carbohydrate substrates [methyl 4,6-O-(phenylmethylene)-1-thio-α-D-glucopyranoside 1a, 1-cyano-1-deoxy-4,6-O-(phenylmethylene)-α-D-galactopyranose 2a, methyl α-D-xylopyranoside 3a, methyl β-D-arabinopyranoside 4a, and methyl 5-O-(tert-butyldiphenylsilyl)-α-D-ribofuranoside 5a], selective mono-triflation was achieved where the reacting hydroxyl is cis and vicinal to a heteroatom. 相似文献
18.
19.
室温离子液体增塑的纳米复合聚合物电解质研究 总被引:2,自引:0,他引:2
在室温离子液体N-乙基-N'-甲基咪唑四氟硼酸盐(EMIBF4)增塑的凝胶聚合物电解质中加入氧化铝纳米粒子, 制备了一种纳米复合聚合物电解质(nanocomposite polymer electrolyte, NCPE). 通过示差扫描量热(DSC)、X射线衍射(XRD)、热重分析(TGA)、电化学阻抗谱(EIS)等手段对其进行了表征. 结果显示, 随着氧化铝纳米粒子含量的增加, NCPE的结晶度降低, 离子导电率升高. 但是, 纳米粒子的加入量过大时反而引起NCPE的离子导电率降低. 当纳米粒子填充量为w=10%时, NCPE具有最高的室温离子导电率1.25×10-3 S•cm-1. 相似文献
20.
Han-Ping Zhang Hong Zhou Zhi-Quan Pan Xiang-Gao Meng You Song 《Transition Metal Chemistry》2008,33(1):55-60
A novel linear trinuclear copper(II) complex bridged by phenoxy and benzyloxy oxygen atoms ([Cu3L2](ClO4)2 · (CH3CN)2, L = C11H13BrN2O2
2−) was synthesized and the crystal structure of the complex was determined by X-ray diffraction technique. The crystal structure
of the complex contains a linear trinuclear array of copper(II) ions in which the central copper(II) ion is in an octahedron
coordination sphere and lies on an inversion center of the molecule, the terminal ones are in an identical square pyramid
structure. Variable-temperature magnetic data indicate that the complex displays a strong antiferromagnetic coupling with
J = −270(8) cm−1 between the metal ions. 相似文献