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1.
Slootweg JC Vlaar MJ Vugts DJ Eichelsheim T Merhai W de Kanter FJ Schakel M Ehlers AW Lutz M Spek AL Lammertsma K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(16):4808-4818
Reaction of the transient phosphinidene complexes R-P=W(CO)5 with N-substituted-diphenylketenimines leads unexpectedly to the novel 2-aminophosphindoles, as confirmed by an X-ray crystal structure determined for one of the derivatives. Experimental evidence for a methylene-azaphosphirane intermediate was found by using the iron-complexed phosphinidene iPr2N-P=Fe(CO)4, which affords the 2-aminophosphindole together with the novel methylene-2,3-dihydro-1H-benzo[1,3]azaphosphole. Analysis of the reaction pathways with DFT indicates that the initially formed methylene-azaphosphirane yields both phosphorus heterocycles by way of a [1,5]- or [1,3]-sigmatropic shift, respectively, followed by a H-shift. Strain underlies both rearrangements, which causes these remarkably selective conversions that can be tuned by changing the substituents. 相似文献
2.
G. A. Olah G. K. Surya Prakash P. Donald Katherine B. Loker Koop Lammertsma 《Research on Chemical Intermediates》1989,12(2):141-159
In this short review we have shown the importance of protosolvation of onium ions (containing non-bonded pairs of electrons)
in superacid catalyzed reactions. Such activation can result in unusual reactions such as aromatic alkylation with Meerwein’s
salts, aliphatic nitration with nitronium ion, alkylation of saturated hydrocarbons, greatly enhanced activity of acyl cations,
etc. Possibly such phenomena may be operative in hydroxylation reactions using protonated hydrogen peroxide in strong acid
solutions. Even the reactivity of halonium ions could be enhanced by protosolvation. Consequently, electrophilic protosolvation
may play a significant role in strogg acid catalyzed reactions. 相似文献
3.
Vlaar MJ Lor MH Ehlers AW Schakel M Lutz M Spek AL Lammertsma K 《The Journal of organic chemistry》2002,67(8):2485-2493
Six novel dispirophosphirane complexes have been synthesized from the reaction of bicycloalkylidenes with the electrophilic phosphinidene complex PhPW(CO)(5). They contain a central phosphirane ring, which is spirofused on one side to a cyclopropane or cyclobutane ring and on the other side with a three-, four-, five-, or six-membered ring. Their crystal structures and MP2/6-31G-computed geometries for simplified parent systems suggest that spirofusion with small rings results in a tightening of the central three-membered phosphaheterocycle, while spirofusion with larger rings results in a relaxation of the phosphirane geometry. Similar theoretical predictions are made for the corresponding annulated hydrocarbons. Strain energies for both the hydrocarbon and phosphorus series of structures have been calculated at G3(MP2). Whereas the [3]triangulane hydrocarbon and phospha[3]triangulane have a significant excess strain of 8.1 and 5.2 kcal/mol per spiroatom, respectively, the excess strain for systems spirofused with larger rings are negligible for the hydrocarbons and even negative for the phosphorus-containing species because of hyperconjugative stabilization. 相似文献
4.
Tautomeric isomers and conformers of 2-nitrovinyl alcohol (1), 2-nitrovinylamine (2), and 1-nitro-propene (3) are reported at the MP2 and B3LYP levels of theory, using the 6-31G* basis set, with energy evaluation at B3LYP/6-311+G** and G2MP2. The nitroalkenes are the global minima on their respective potential energy surfaces. The barriers for the concerted 1,5-H transfer to the corresponding nitronic acids amount to only 5.0 kcal/mol for 1, 13.2 kcal/mol for 2, and a sizable 37.8 kcal/mol for 3. Whereas the aci-nitro tautomer of 2-nitrovinyl alcohol is easily accessible, beta-iminonitronic acid has little kinetic stability. H-bonding is a strong stabilizing factor in these nitroalkenes, estimated at 7.0 and 3.7 kcal/mol for the OH and NH2 derivatives, respectively, while its stabilization in their nitronic acids amounts to as much as 13 kcal/mol. The H-bonds are evident from the very short O...H and N...H distances and are characterized by bond critical points. The NO2 substituent effect of about 11.4 kcal/mol at G2MP2 on both the classical keto <==> enol and imine <==> enamine tautomeric processes stabilizes the nitroethylene derivatives. The keto, imine, and vinyl substituent effects at G2MP2 on the nitro <==> aci-nitro tautomeric process are also determined as are their pi-resonance components. The substituents have a large influence on the ionization energies of the nitroethylene derivatives. 相似文献
5.
6.
Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon 下载免费PDF全文
Tom van Dijk Dr. Sebastian Burck Mark K. Rong Amos J. Rosenthal Dr. Martin Nieger Dr. J. Chris Slootweg Prof. Dr. Koop Lammertsma 《Angewandte Chemie (International ed. in English)》2014,53(34):9068-9071
Readily accessible nitrilium triflates are convenient imine building blocks for the expedient synthesis of a novel class of 1,3‐P,N ligands as demonstrated for the reaction with primary phosphanes. This procedure allows variation of all substituents. X‐ray crystal structures are reported for nitrilium ions, phosphaamidines, and three phosphaamidinate complexes. The lithium phosphaamidinate is N coordinated and its reaction with [AuCl(tht)] (tht=tetrahydrothiophene) gives a unique P‐bridged gold trimer, while a P,N‐bidentate complex results from [{RhCl(cod)}2]. The nitrilium ion methodology allows extension of the 1,3‐P,N motive to bis(imino)phosphanes, which are the neutral phosphorus analogues of the valuable β‐diketiminate ligand. 相似文献
7.
8.
9.
J. C. Koop 《Annals of the Institute of Statistical Mathematics》1976,28(1):461-467
Summary The bias of ratio estimators based on a simple random sample ofn units drawn from a finite universe ofN units, and reconstructed according to, or in ways similar to Quenouille's method, is of order 1/n only ifN≧n
2, and of order 1/n
Q
, where 1<Q<2, ifN<n
2. Further it is shown that the device of splitting samples, either for bias reduction and/or convenience of variance estimation,
except for the special case noted in the paper, yields estimators that are inefficient and can be improved. 相似文献
10.
V. M. Aulchenko M. N. Achasov S. E. Baru K. I. Beloborodov A. V. Berdyugin A. G. Bogdanchikov A. V. Bozhenok A. D. Bukin D. A. Bukin A. V. Vasilev V. B. Golubev T. V. Dimova V. P. Druzhinin V. N. Ivanchenko I. A. Koop A. A. Korol S. V. Koshuba A. P. Lysenko A. V. Otboev E. V. Pakhtusova A. A. Salnikov S. I. Serednyakov V. A. Sidorov Z. K. Silagadze V. V. Shary Yu. M. Shatunov 《Journal of Experimental and Theoretical Physics》2003,97(1):24-33
The process e + e ? → η′γ, η′ → η π0π0, η → γγ is investigated by an SND detector in experiment on a VEPP-2M equipment with colliding electron-positron beams. The analysis of experimental data yields a value of B(? → η′γ)=(6.7 ?4.2 +5.0 ±1.5)×10?5 for the decay probability. Taking into account a previous measurement of this quantity by an SND detector in the decay channel η′ → π+π?η, one finally obtains B(?→η ′γ)=(6.7 ?2.4 +2.8 ±0.8)×10?5. 相似文献