全文获取类型
收费全文 | 85篇 |
免费 | 1篇 |
国内免费 | 8篇 |
专业分类
化学 | 74篇 |
晶体学 | 3篇 |
综合类 | 1篇 |
物理学 | 16篇 |
出版年
2024年 | 1篇 |
2023年 | 11篇 |
2020年 | 2篇 |
2015年 | 1篇 |
2014年 | 1篇 |
2013年 | 20篇 |
2012年 | 2篇 |
2011年 | 2篇 |
2010年 | 1篇 |
2009年 | 3篇 |
2008年 | 5篇 |
2007年 | 5篇 |
2006年 | 1篇 |
2005年 | 2篇 |
2004年 | 6篇 |
2003年 | 1篇 |
2002年 | 1篇 |
2001年 | 2篇 |
1999年 | 2篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1993年 | 5篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有94条查询结果,搜索用时 31 毫秒
1.
自1971年Peacock等首次合成出以杂多阴离子为配位体的镧系元素的一些杂多配合物[Ln(XW_(11)O_(39))_2]~(n-)(X=P,Si)以来,Zuhairi等又合成出镧的一些其它杂多钨酸盐[La(XW_(11)O_(39))_2]~(n-)(X=B,Si,Ge,P,As)。 为开发新型的镧系元素催化剂,我们系统地研究了镧系元素的杂多钨酸盐和杂多钼酸盐。本文报道有关K_(11)[Ln(PW_9Mo_2O_(39))_2]·nH_2O(Ln=La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Er,Yb)的合成及性质的研究结果。 相似文献
2.
Tris{[tri(2-methylphenyl)phosphine]gold(I)}-, tris{[tri(2,4,6-trimethylphenyl)phosphine]gold(I)}- and tris{[tri(cyclohexyl)phosphine]gold(I)}-oxonium tetra-fluoroborate ( 1?3 ) have been prepared from the corresponding (phosphine)gold(I) chlorides, silver oxide, and sodium tetrafluoroborate in acetone. These oxonium salts are excellent aurating agents for primary amines. Thus in the reaction with 1, t -butylamine tBuNH2 and aniline PhNH2 are readily converted into the tri nuclear imino complexes {[(2-MeC6H4)3P]Au}3NtBu+BF4? ( 4 ) and {[(2-MeC6H4)3P]Au}3NPh+BF ( 5 ) in high yields. With 3 , both aniline and 8-amino-quinoline also give the tri nuclear complexes, i.e. {[(c-C6H11)3P]Au}3 NPh+BF ( 6 ) and {[(c-C6H11)3P]Au}3N(C9H6N)+BF ( 7 ). Auration of aniline with the most sterically hindered reagent 2 yields only the bi nuclear complex {[2,4,6-Me3C6H2)3P] · Au}2N(Ph)H+BF ( 8 ). The reagents 1?3 and the Products 4 – 8 have been characterized by analytical and NMR spectroscopic data, and the crystal structures of compounds 4 and 6 have been determined by single crystal x-ray diffraction. In the cations of 4 , a triangle of gold atoms with short Au — Au contacts [3.036(1), 3.107(1), and 3.214(1) Å] forms a steep pyramid with the nitrogen atom, in which the angles Au? N? Au are all much smaller than the tetrahedral standard of 109.7°: 94.8(4), 98.1(4), and 103.0(4)°. This triangular Au3 unit is staggered relative to the three methyl groups of the tBu substituent at nitrogen. The results for 6 are similar [Au — Au: 3.037(1), 3.071(1), and 3.222(1) Å; Au? N? Au: 95.3(3), 96.5(3), and 103.6(3)°]. Variable temperature NMR studies of compounds 3 and 8 show hindered rotation of the mesityl groups about the P? C bonds of the ligands originating from the steric congestion within each tertiary phosphine. 相似文献
3.
Synthesis and Crystal Structure of Cadmium Dodecahydro closo‐Dodecaborate Hexahydrate, Cd(H2O)6[B12H12] Through neutralization of the aqueous free acid (H3O)2[B12H12] with cadmium carbonate (CdCO3) and after isothermic evaporation of the resulting solution, colourless lath‐shaped single crystals of Cd(H2O)6[B12H12] are obtained. Cadmium dodecahydro closo‐dodecaborate hexahydrate crystallizes at room temperature in the monoclinic system (space group: C2/m) with the lattice constants a = 1413.42(9), b = 1439.57(9), c = 749.21(5) pm and β = 97.232(4)° (Z = 4). The crystal structure of Cd(H2O)6[B12H12] can be regarded as a monoclinic distortion variant of the CsCl‐type structure. Two crystallographically different [Cd(H2O)6]2+ octahedra (d(Cd–O) = 227–230 pm) are present which only differ in their relative orientation. The intramolecular bond lengths for the quasi‐icosahedral [B12H12]2? cluster anions range in the intervals usually found for dodecahydro closo‐dodecaborates (d(B–B) = 177–179 pm, d(B–H) = 103–116 pm). The hydrogen atoms of the [B12H12]2? clusters have no direct coordinative influence on the Cd2+ cations. Due to the fact that no “zeolitic” crystal water molecules are present, a stabilization of the lattice takes place mainly via the B–Hδ?···+δH–O hydrogen bonds. 相似文献
4.
Pentafluorethyl Sulfurtrifluoride: Synthesis and Reactions By oxidation of (C2F5S?)2 ( 1 ) with AgF2 at 0°C a mixture of C2F5SF3 ( 2 ) and C2F5SF5 ( 3 ) besides C2F5S(O)F ( 4 ) is formed. With elemental fluorine only 3 is isolated, an intermediate in this reaction is (C2F5SF4?)2 ( 5 ). At ?40 to ?30°C the mixture of 2, 3 and 4 was reacted with TASF and AsF5, to give TAS+ C2F5SF4? ( 6 ), TAS+ C2F5S(O)F2? ( 7 ) and C2F5SF2+AsF6? ( 8 ), respectively. While 6 and 7 decompose rapidly in solution even at low temperatures, of thermally stable 8 the solid state structure was determined by x-ray diffraction. 相似文献
5.
Preparation and Crystal Structure of the Pnictide Oxides Na2Ti2As2O and Na2Ti2Sb2O Na2Ti2As2O and Na2Ti2Sb2O were synthesized in form of very easily hydrolysed metallic-grey powders by reaction of Na2O and TiAs resp. TiSb in sealed tantalum tubes under argon. The tetrahedral bodycentered crystallizing compounds from a modified anti-K2NiF4 structure type [1] (also called Eu4As2O-type [2,3]), space group I4/mmm (no. 139), with the lattice constants for Na2Ti2As2O: a = 407.0(2) pm, c = 1528.8(4) pm and for Na2Ti2Sb2O: a = 414.4(0) pm, c = 1656.1(1) pm. Magnetic measurements of powder samples of Na2Ti2Sb2O show antiferromagnetic interaction within the Ti—O-layers. Superconductivity was not found by ac-shielding method down to 4 K. 相似文献
6.
Frank Hoffmann Lothar Jäger Carola Griehl 《Phosphorus, sulfur, and silicon and the related elements》2013,188(2):299-309
The reactions of diphenoxyphosphoryl chloride ((PhO) 2 P(O)Cl) and different chlorophosphonium salts ([R 3 PCl]X, R = (CH 3 ) 2 N, pyrrolidine, X = PF 6 m , BF 4 m ), respectively, with 7-aza-1-hydroxybenzotriazole (HOAt), 1-hydroxybenzotriazole (HOBt), hydroximinomalonitrile (HOxDCO), and ethyl hydroximinocyanoacetate (HOxO) are described. The structures of the new compounds, which are useful coupling reagents for epimerization-free peptide segment condensation, are discussed on the basis of their 1 H, 13 C, 31 P NMR, and IR spectra. The reactions of (PhO) 2 P(O)Cl lead to mixtures of O - and N -phosphorylated isomers of varying ratios. Contrary, reactions of chlorophosphonium salts yield exclusively one isomer. 相似文献
7.
Christian Reichardt Hans-Peter Erfurt Klaus Harms 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5):1081-1092
Attempts at the oxidation of 3-ethyl-2-methylbenzothiazolium salt 2 with a variety of oxidizing reagents did not lead to the desired isochiral S -oxide 3 or achiral S , S -dioxide 4 , in some cases, however, unexpectedly to the ring-opened dimeric 2,2'-di( N -ethyl-acetamino)substituted diphenyl disulfane 5 , the molecular structure of which was confirmed by x-ray analysis. The synthesis of 2-methylbenzothiazole- S , S -dioxide 14 , reported by Zincke et al. in 1915, turned out to be not reproducible. \centerline{\epsfbox{:art:fig-01.jpg}} 相似文献
8.
An ESR study has been made on the course of grafting of tetrafluoroethylene onto polyethylene. Alkyl and allyl radicals trapped in the polymers were measured under various grafting conditions. It was observed that alkyl radicals decay very rapidly when monomers are in contact with the irradiated polymer, while allyl radicals decay very slowly even in the presence of monomers as in the decay of radicals in irradiated polymers without monomers. The effect of pre-irradiation temperature on grafting was also studied, and the rate of grafting was found to be much faster for lower pre-irradiation temperatures. From these experimental results it was concluded that alkyl radicals play an important Tole in the initiation reaction of grafting. 相似文献
9.
Physicochemical and adsorption properties of hypercross‐linked polystyrene with ultimate cross‐linking density
下载免费PDF全文
![点击此处可从《Journal of separation science》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Maria P. Tsyurupa Zinaida K. Blinnikova Yuri A. Borisov Mikhail M. Ilyin Tamara P. Klimova Kiril V. Mitsen Vadim A. Davankov 《Journal of separation science》2014,37(7):803-810
The paper describes unexpected properties of hypercross‐linked polystyrenes with ultimate cross‐linking degrees of 300, 400, and 500%, where three, four, or five methylene links, respectively, could bind each polystyrene phenyl ring to its spacious neighbors. The polymers exhibit a strong electron spin resonance signal, unusual spectra in IR, UV, and visible ranges, and they are not typical dielectrics. The nonfunctionalized hypercross‐linked polymers absorb significant amounts of inorganic acids, salts, and bases due to interactions of protons or other cations with electron‐donating fragments of the aromatic network with the high extent of mutual connectivity and also due to dispersion interactions of anions with the polymer matrix. 相似文献
10.
Jiang Wang Megan E. Hoerrner Mary P. Watson Daniel J. Weix 《Angewandte Chemie (International ed. in English)》2020,59(32):13484-13489
While ketones are among the most versatile functional groups, their synthesis remains reliant upon reactive and low‐abundance starting materials. In contrast, amide formation is the most‐used bond‐construction method in medicinal chemistry because the chemistry is reliable and draws upon large and diverse substrate pools. A new method for the synthesis of ketones is presented here that draws from the same substrates used for amide bond synthesis: amines and carboxylic acids. A nickel terpyridine catalyst couples N‐alkyl pyridinium salts with in situ formed carboxylic acid fluorides or 2‐pyridyl esters under reducing conditions (Mn metal). The reaction has a broad scope, as demonstrated by the synthesis of 35 different ketones bearing a wide variety of functional groups with an average yield of 60±16 %. This approach is capable of coupling diverse substrates, including pharmaceutical intermediates, to rapidly form complex ketones. 相似文献