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51.
Sanjeev K. Garg 《Tetrahedron letters》2005,46(10):1721-1724
Copper(II) tetrafluoroborate has been found to be a new and highly efficient catalyst for Michael addition of thiols to α,β-unsaturated carbonyl compounds under solvent-free conditions and in H2O at room temperature. The reactions are very fast and are completed in 2 min to 1 h affording high yields. The rate of thiol addition was dependent on the steric hindrance at the β-carbon of the α,β-unsaturated carbonyl substrate. In the case of chalcones, the reactions are best carried out in MeOH as solvent. 相似文献
52.
Determination of carbonyl compounds in air by HPLC using on-line analyzed microcartridges,fluorescence and chemiluminescence detection 总被引:1,自引:0,他引:1
Summary Sensitive and selective detection of dansylhydrazones of atmospheric carbonyl compounds (aldehydes and ketones) can be achieved using high performance liquid chromatography (HPLC) with fluorescence or chemiluminescence detection. The carbonyl compounds are derivatized by drawing air through small glass cartridges packed with porous glass particles impregnated with dansylhydrazine. After sampling, the contents of the cartridges are analyzed on-line by using a small plug of water (200 L) to transfer and focus the hydrazone derivatives at the head of a HPLC column. Greatly increased sensitivity over traditional methods derives from 1) analysis of the entire contents of the sampling cartridge, and 2) detection by fluoresence or peroxyoxalate chemilum-inescence. Results are compared for photo-initiated and H2O2-initiated peroxyoxalate chemiluminescence. This novel and practical system enables the detection of sub-ppbv concentrations of formaldehyde, acetaldehyde, acetone and higher carbonyls in air using relatively short sampling times. 相似文献
53.
The results of kinetic studies on ligand substitution in [M3(CO)11X]– complexes (M = Ru, Os; X = Cl, Br, I) are summarized. The [Os3(CO)11X]– complexes react with PPh3 under mild conditions to initially yield monosubstituted products [Os3(CO)10(PPh3)X]–. The rate of CO substitution obeys a first-order equation with respect to the concentration of the complex and does not depend on the ligand concentration. The rates of the reactions decrease in the order Cl > Br > I withH values increasing from 15 to 18 kcal mol–1 and S
values varying from –19 to –13 cal mol–1 K–1. The enhanced reactivities of these complexes as well as the low activation energies and negative activation entropies are discussed in terms of the effects of -X bridge formation on the transition state of the reaction. Reactions of PPN[Ru3(CO)11–x
(Cl)] (PPN is the bis(triphenylphosphine)iminium cation;x=0, 1) and PPN[Ru3(CO)9(3-I)] with alkynes are also reported. The reactivities of alkynes follow the order BuCCH PhCCH EtCCEt PhCCPh. The higher rates of the reactions of monosubstituted acetylenes compared with those of their disubstituted analogs are explained by agostic interaction between the metal atom and the C-H bond in the reaction transition state and by steric effects. The results obtained attest that the reaction with alkynes occursvia intermediates containing halide bridges and that 3-halide complexes are more reactive than 2-halide complexes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1540–1545, September, 1994.This work was supported by a Presidential Grant from Northwestern University. One of the authors (F. Basolo) wishes to thank Academician M. E. Vol'pin for the invitation to participate in the Workshop The Modern Problems of Organometallic Chemistry (INEOS-94) and Academician O. M. Nefedov for the invitation to publish a review in theRussian Chemical Bulletin. 相似文献
54.
The complex (1) has been prepared and its structure determined. Complex1 is the first stable thioether derivative of a metal carbonyl containing only cobalt as metal. It crystallizes in the monoclinic P21/c space group, witha = 13.975( 4 ),b = 11.363( 3 ),c = 14.686(2)A, = 112.25(2)°,V = 2158.5(7)A3.Z = 4. The solution using direct methods and the anisotropic refinement of all nonhydrogen atoms led toR = 0.039,wR = 0.041 for 3296 reflections with F> 4.0(F) Analogous but less stable complexes are formed with 1,6-diphenyl-2,5-dithiahexane and the crown thioether 1,4,7-trithiacyclonane, the latter functioning either as a bidenlate or a tridentate ligand. 相似文献
55.
Tsuneyoshi Tominaga 《Journal of fluorine chemistry》2004,125(1):67-71
Synthetic routes for α-trifluoromethylated carbonyl compounds based on the aldol reaction of silylenol ether and the palladium(0) catalyzed reaction using by 4,4,4-trifluorobutan-2-one are described. 相似文献
56.
Ntaoleng M. Makunya Reinout Meijboom Alfred Muller 《Journal of organometallic chemistry》2005,690(18):4159-4167
Cyclopentadienyldicarbonylmethyliron, [CpFe(CO)2Me] (1), undergoes migratory carbonyl insertion under the influence of isosteric phosphine ligands P(4-FC6H4)3 and P(4-MeC6H4)3. The products of the reaction, [CpFe(CO)(COMe)P(4-FC6H4)3] (2a) and [CpFe(CO)(COMe)P(4-MeC6H4)3] (2b), were characterised by X-ray crystallography. In both structures, the iron atom adopts a pseudo octahedral coordination geometry. Fe-P bond distances are the same at 2.1932(8) Å in 2a and 2b, respectively. Thus, contrary to what was expected, X-ray data could not be used to quantitatively differentiate between the two phosphine ligands in 2a and 2b. Therefore, additional spectroscopic techniques such as IR and NMR were employed. Similarly, the Fe-C bond lengths of the carbonyl (Fe-CO) and acetyl (Fe-COMe) are 1.748(3) and 1.955(3) in 2a, and 1.744(3) and 1.951(3) Å in 2b, respectively.The migratory carbonyl insertion was studied by NMR, IR, and UV-vis spectroscopies to determine the mechanism and the rate law. Results from NMR spectroscopy show that the formation of the product is accompanied by oxidation of the corresponding phosphine ligand. An increase in the reactivity of migratory carbonyl insertion for P(4-MeC6H4)3 was observed when the solvent was changed from CH2Cl2 to MeCN. The kinetic data showed that P(4-MeC6H4)3 reacts faster than P(4-FC6H4)3. 相似文献
57.
Meyer F Demeshko S Leibeling G Kersting B Kaifer E Pritzkow H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(5):1518-1526
Pyrazolate-based dinucleating ligands with thioether-containing chelate arms have been used for the synthesis of a family of novel tetranuclear nickel(II) complexes [L2Ni4(N3)3(O2CR)](ClO4)2 that incorporate three azido bridges and one carboxylate (R = Me, Ph). Molecular structures have been elucidated by X-ray crystallography in four cases, revealing Ni4 cores with a unique topology in which two of the azido ligands adopt an unusual mu3-1,1,3 bridging mode. The compounds were further characterized by mass spectrometry, IR spectroscopy, and variable-temperature magnetic susceptibility measurements. Magnetic data analyses indicate a combination of significant intramolecular ferromagnetic and antiferromagnetic exchange interactions that give rise to an overall S(T) = 0 ground state. The sign and the magnitude of the individual couplings have been rationalized in the framework of the common magnetostructural correlations for end-to-end and end-on azido linkages, suggesting that these correlations also remain valid for the respective fragments of multiply bridging mu3-1,1,3 azido ligands. 相似文献
58.
Nigel T. Lucas Marie P. Cifuentes Lam T. Nguyen Mark G. Humphrey 《Journal of Cluster Science》2001,12(1):201-221
The new phosphines Ph2PC6H4-4-CCR [R=SiMe3 (1), H (2)] have been used to prepare Ru3(CO)9(Ph2PC6H4-4-CCSiMe3)3 (4) and Ru(CCC6H4-4-PPh2)(PPh3)2(-C5H5) (3), respectively, the latter with a pendent phosphine. Reaction of 4 with carbonate or fluoride affords Ru3(CO)9(Ph2PC6H4-4-CCH)3 (5) with pendent terminal alkynyl groups, the identity of which was confirmed by a structural study. Reaction of 5 with [Ru(NCMe)(PPh3)2(-C5H5)]PF6 or reaction of Ru3(CO)12 with 3 gives Ru3(CO)9{(Ph2PC6H4-4-CC)Ru(PPh3)2(-C5H5)}3 (6). Complexes 3–6 have been studied by cyclic voltammetry. Proceeding from Ru3(CO)12 to 4 or 5 shifts the cluster-centred reduction to more negative potential and affords facile cluster-centred oxidation. Proceeding from 4/5 and 3 to 6 results in similarly-located cluster-centred reduction and peripheral ruthenium-centred oxidation, but results in a lack of observable cluster-centred oxidation. Crystal data for 5·C6H14: space group P¯1, a=12.760(1) Å, b=17.077(1) Å, c=17.924(2) Å, =108.656(5)°, =96.344(5)°, =93.523(5)°, V=3658.4(6) Å3, Z=2, R=0.078, Rw=0.105 for 5008 reflections [I>2.00(I)]. 相似文献
59.
XIAO Feng-Shou XU Ru-Ren HE Ya-Nan Department of Chemistry Jilin University Changchun Jilin China 《中国化学》1994,12(3):258-264
NaY zeolite entrapped Ru3(CO)12 cluster has been synthesized from RuCl3 ion-exchanged NaY, which is well characterized by IR and Raman spectroscopies and CO chemisorp-tion. When the Ru3+/NaY sample is heated from 298 K to 393 K for 25 h and for 10 h at 393 K, the sample colour changes from dark to brown-yellow. The in situ infrared spectrum exhibits absorption bands at 2130, 2064, 2040, 2017, 1990, 1953 and 1925 cm-1. The bands at 2130 cm-1 arises from the Runm+(CO)l m =1-3;n = 1 - 3; l = 1-12). The bands at 2064, 2040, 2017 and 1990 cm-1 are proposed to be associated with the Ru3(CO)12/NaY, which are close to Ru3(CO)12 crystalline. Furthermore, the Raman results provide bands at 150 and 185 cm-1, which can be attributed to Ru-Ru bonds of the sample as in the case of Ru3(CO)12 crystalline, for which the A1' Ru-Ru stretching mode is assigned to 185 cm-1 and E1' Ru-Ru stretching mode is assigned to a band at 150 cm-1, respectively. CO chemisorption of [Ru3]/NaY gives a CO/Ru ratio of 3.85, which is simila 相似文献
60.
用ab initio方法研究NaN_3的几何构型、电子结构和热力学、动力学性质 总被引:2,自引:0,他引:2
用abinitioMO方法,在MP2(ful)/6311G水平下,全优化计算了叠氮化钠(NaN3)分子的线状和环状两种稳定构型及其转化过渡态的几何参数、电荷分布、分子总能量和振动频率,并研究了它们的热力学性质及转化速率常数和平衡常数.结果表明,线状比环状构型稍稳定(能量低6.04kJ/mol);两者相互转化的能垒分别为13.15kJ/mol(线型→环状)和7.11kJ/mol(环状→线型).热力学和动力学计算均表明:NaN3通常主要以线型结构存在(占85%以上),且随温度升高而增多(在1000K大于91%). 相似文献