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排序方式: 共有271条查询结果,搜索用时 46 毫秒
261.
Dr. Marian Olaru Daniel Duvinage Dr. Enno Lork Dr. Stefan Mebs Prof. Dr. Jens Beckmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(65):14758-14761
Fluoride abstraction from bis-m-terphenylelement fluorides (2,6-Mes2C6H3)2EF (E=P, As) generated the highly reactive phosphenium ion [(2,6-Mes2C6H3)2P]+ and the arsenium ion [(2,6-Mes2C6H3)2As]+, which immediately underwent intramolecular electrophilic substitution and formation of an 1,2,4-trimethyl-6-mesityl-5-m-terphenyl-benzo[b]phospholium ion and an 1,2,4-trimethyl-6-mesityl-5-m-terphenyl-benzo[b]arsolium ion, respectively. The formation of the latter involved a methyl group migration from the ortho-position of a flanking mesityl group to the meta-position. This reactivity of [(2,6-Mes2C6H3)2E]+ (E=P, As) is in sharp contrast to the related stibenium ion [(2,6-Mes2C6H3)2Sb]+ and bismuthenium ion [(2,6-Mes2C6H3)2Bi]+, which have been recently isolated and fully characterized (Angew. Chem. Int. Ed. 2018, 57 , 10080–10084). On the basis of DFT calculations, a mechanism for the rearrangement of the phosphenium and arsenium ions into the phospholium and arsolium ions is proposed, which is not feasible for the stibenium and bismuthenium ions. 相似文献
262.
刘晓静 《原子与分子物理学报》2017,34(6)
采用密度泛函理论研究了Cl对气态亚硝酸(HONO)直接提取氢的反应机理。在B3LYP/6-311G(d,p)水平上,优化得到了反应途径上的反应物、中间体、过渡态和产物的几何构型;通过频率分析对各分子构型进行了确认;并利用QCISD(T)方法计算了各分子单点能量。计算结果表明,HONO分子具有顺式和反式两种构型;常温条件下,Cl对顺式构型直接提取氢的反应竞争性具有明显优势,其主要反应途径为:cis-HONO+Cl→cis-M1→cis-TS→cis-M2→HCl+NO2。 相似文献
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Long Zhao Ralf I. Kaiser Wenchao Lu Musahid Ahmed Mikhail M. Evseev Eugene K. Bashkirov Valeriy N. Azyazov Christina Tnshoff Florian Reicherter Holger F. Bettinger Alexander M. Mebel 《Angewandte Chemie (International ed. in English)》2020,59(28):11334-11338
A representative, low‐temperature gas‐phase reaction mechanism synthesizing polyacenes via ring annulation exemplified by the formation of pentacene (C22H14) along with its benzo[a]tetracene isomer (C22H14) is unraveled by probing the elementary reaction of the 2‐tetracenyl radical (C18H11.) with vinylacetylene (C4H4). The pathway to pentacene—a prototype polyacene and a fundamental molecular building block in graphenes, fullerenes, and carbon nanotubes—is facilitated by a barrierless, vinylacetylene mediated gas‐phase process thus disputing conventional hypotheses that synthesis of polycyclic aromatic hydrocarbons (PAHs) solely proceeds at elevated temperatures. This low‐temperature pathway can launch isomer‐selective routes to aromatic structures through submerged reaction barriers, resonantly stabilized free‐radical intermediates, and methodical ring annulation in deep space eventually changing our perception about the chemistry of carbon in our universe. 相似文献
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Ab initio and density functional theory calculations have been carried out to investigate the reaction of hydroxyl radical (OH) and 1,1,1-trichloroethane (CH3CCl3). The potential energy surface has been given according to the relative energies calculated at the MP2/cc-pVTZ level after the spin projection (PMP2). Five reaction channels were identified and the intramolecular hydrogen bonding was observed in some transition state structures. The barrier heights and reaction enthalpies calculated for all possible channels show that the hydrogen abstraction channel is predominant kinetically and thermodynamically. The contribution from other channels was predicted to be minor. 相似文献
268.
Randolph K. Belter 《Journal of fluorine chemistry》2011,132(5):318-322
At temperatures around 400 °C, nitrogen trifluoride (NF3) readily reacts with benzylic substrates. Products vary with the substrate, but are all the result of difluoroamination at the benzylic position. Toluene and ethylbenzene produce benzonitrile. Cumene produces α-methylstyrene. Diphenylmethane produces benzanilide. Little or no direct fluorination or radical dimerization is observed. 相似文献
269.
报道了利用原位电子自旋共振(ESR)技术研究对二嗪N,N′-二氧化物光解的结果。研究结果表明,化合物5,6,7和8通过光还原过程从溶剂分子夺取氢原子分别生成稳定的自由基,记录出它们分辨良好的ESR谱。文中还讨论了对二嗪N,N′-二氧化物的光化学反应的自由基机理。 相似文献
270.
The synthesis and properties of the new metal complexes 1 , 6 – 12 with alkoxysilylmethy substituents (RO–SiR′2–CH2–MLn) is described. The complexes 14 , 15 and 18 with a chloromethylsiloxy ligand were also prepared. These molecules should serve as starting compounds for the synthesis of metallasilaoxetanes. Several reactions which should lead to these new metallacycles have been performed, but it was never possible to isolate them or to proof their existence spectroscopically. However, chloride abstraction from (C5H5)2Ti(Cl)CH2Si(CH3)2OtBu ( 7 ) by silver cations led to the activation of the Si–O–R group. This indicates an interaction of the oxygen atom with the metal atom, but there was no proof for the intermediate formation of a four membered metallacycle. 相似文献