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61.
Marc Karl Klaus Harms Gerd Seybert Werner Massa Stefan Fau Gernot Frenking Kurt Dehnicke 《无机化学与普通化学杂志》1999,625(12):2055-2063
Deprotonation Reactions of Silylated Amido Complexes of Rare Earth Elements The deprotonation of the rare earth element-tris(bistrimethylsilyl)amides Ln[N(SiMe3)2]3 of scandium, ytterbium, and lutetium with sodium-bis(trimethylsilyl)amide in THF leads to the complexes [Na(THF)3LnCH2SiMe2NSiMe3{N(SiMe3)2}2] [Ln = Sc ( 1 ), Yb ( 2 ), and Lu ( 3 )]. According to crystal structure analyses of 1 and 2 the metal atoms Sc and Yb are constituents of planar LnCSiN four-membered rings. At the same time, the C atom of the CH2 group is coordinated with the sodium ion in a linear axis Ln–C–Na; the sodium ion obtains a distorted tetrahedral arrangement by three THF molecules. The equatorial positions of the methylene-C atom, which is coordinated in a trigonal bipyramidal fashion, are occupied by the two H atoms and the Si atom of the four-membered ring. 2.6-dimethylbenzoisonitrile can be inserted into the Yb–CH2 bond of 2 and the new five-membered heterocylce YbNCSiN originates, the exocyclic CH2 group of which enters into a C–C coupling with the centrosymmetric dimer 4 while the ytterbium undergoes reduction. At the same time, sodium-7-methyl indolate is formed, which together with [NaN(SiMe3)2(THF)2] forms the centrosymmetric dimeric molecular aggregate [NaN(SiMe3)2(THF)2Na(C9H16N)]2 ( 5 ). 1 : Space group P21/n, Z = 8, lattice dimensions at –80 °C: a = 2941.4(2), b = 1205.5(1), c = 2952.4(3) pm; β = 113.455(8)°; R1 = 0.0625. 2 : Space group P21/n, Z = 8, lattice dimensions at –80 °C: a = 2943.9(1), b = 1219.5(1), c = 2944.3(1) pm; β = 113.372(4)°; R1 = 0.0361. 4 : Space group P 1, Z = 4, lattice dimensions at –80 °C: a = 1117.0(1), b = 1207.5(1), c = 1614.3(2) pm; α = 73.634(10)°, β = 82.091(10)°, γ = 74.391(10)°; R1 = 0.0525. 5 : Space group P21/n, Z = 2, lattice dimensions at –80 °C: a = 1126.7(1), b = 1459.3(1), c = 1741.1(1) pm; β = 96.461(8)°; R1 = 0.0458. Quantum chemical DFT calculations of the scandium model compound [Na(Me2O)3ScCH2SiMe2NSiH3{N(SiH3)2}2] ( 1 M ) give a very large negative charge at the pentacoordinated carbon atom of the four-membered ring that is concentrated in a lone-pair orbital which has mainly p character. The carbon atom interacts with the positively charged scandium atom mainly by Coulombic interactions. 相似文献
62.
63.
Phosphoraneiminato Cluster of Iron. The Crystal Structures of [FeCl(NPEt3)]4, [Fe(C=C–SiMe3)(NPEt3)]4, and [Fe3Cl4{NP(NMe2)3}3] The reaction of iron dichloride with the silylated phosphaneimine Me3SiNPEt3 in the presence of potassium fluoride at 165 ?C leads to the phosphoraneiminato complex [FeCl(NPEt3)]4 ( 1 ). Compound 1 forms black, moisture and oxygen sensitive crystals. According to the crystal structure analysis 1 has a heterocubane structure, in which the iron and the nitrogen atoms of the NPEt3– groups occupy the corners of a distorted cube and form Fe–N–Fe bond angles of 83.1? and N–Fe–N angles of 96.5?. This results in significantly short Fe…Fe contacts of 272.9 pm. The results of magnetic susceptibility measurements in the range of temperatures from 1.8 to 293 K and the 57Fe‐Mössbauer spectra in the range of temperatures from 2 to 300 K are reported. Compound 1 reacts with the lithiated acetylenes LiC=C–CMe3 and LiC=C–SiMe3 in n‐hexane to form the iron‐organic derivatives [Fe(C=C–R)(NPEt3)]4 [R = CMe3 ( 2 a ), R = SiMe3 ( 2 b )] keeping the heterocubane structure. Compounds 2 a and 2 b form crystals which are very reactive and also black. According to the crystal structure analysis 2 b has a Fe4N4 heterocubane structure which is less distorted than that in 1 with bond angles Fe–N–Fe of 85.5? and N–Fe–N of 94.2?. This leads to the longer Fe…Fe contacts of 281.4 pm. With the dimethylamido derivative Me3SiNP(NMe2)3 iron dichloride reacts under conditions similar to those in the synthesis of 1 to form the dark green mixed‐valenced FeII/FeIII cluster [Fe3Cl4{NP(NMe2)3}3] ( 3 ). According to the crystal structure analysis the three iron atoms in 3 are connected via one μ3‐N atom of a NP(NMe2)3– ligand, via two μ‐N atoms of the two remaining phosphoraneiminato ligands, and via one μ‐Cl atom to form an incomplete heterocubane skeleton. 相似文献
64.
David Scheschkewitz Matthias Menzel Matthias Hofmann Paul von Ragu Schleyer Gertraud Geiseler Werner Massa Klaus Harms Armin Berndt 《Angewandte Chemie (International ed. in English)》1999,38(19):2936-2939
Remarkably short distances to the ring plane are shown by the η5-bound lithium ions in the first compound with a triply negatively charged five-membered ring, 1 , which was obtained by reduction of 2 with lithium. R=CH(SiMe3)2, Dur=2,3,5,6-tetramethylphenyl. 相似文献
65.
Intramolecular FeII-catalyzed reactions of various unsaturated alkoxycarbonyl azides are described. The reactions occur in the presence of stoichiometric amounts of trimethyl silyl chloride employing ethanol as the solvent. The corresponding 2-alkenyloxycarbonyl azides 5, 9, 18, 20, 22, and 24 gave the products 7/8, 10/11, 19, 21, 23, and 25 of an olefin chloroamination in moderate to good yields (47-72%). The facial diastereoselectivity of the ring closing C-N-bond forming step is good both in cyclic (20, 24) and in acyclic substrates (5, 18, 22) (>90% ds). The subsequent chlorine atom transfer occurs selectively in cyclic systems (20, 24) and in systems (9b, 18) which exhibit a conformational bias in the postulated radical intermediate 14. The lifetime tau of this elusive intermediate was estimated from the loss of stereochemical information in conformationally unrestricted systems (9a, 22) and from the data obtained with a radical clock (31-->32). 2-Alkynyloxycarbonyl azides 34 and 36 also yield chloroamination products which are obtained exclusively as the (Z)-isomers 35 and 37 (81-99% yield). The products of the tert-butyl-substituted substrates 38 undergo an immediate rearrangement/solvolysis reaction in the reaction mixture and gave the 5-alkoxyoxazolidinones 39 (93-99% yield). 相似文献
66.
Crystal Structure of the Isothiocyanato Complex [Ph3PNH2(OEt2)][Sm(NCS)4(DME)2] Colourless single crystals of [Ph3PNH2(OEt2)][Sm(NCS)4(DME)2] ( 1 ) have been obtained besides of Ph3PS from the reaction of the homoleptic phosphorane iminato complex [Sm(NPPh3)3]2 with carbon disulfide in THF solution, followed by recrystallisation from DME/Et2O. According to the crystal structure analysis 1 consists of [Ph3PNH2]+ cations with the diethylether molecule forming a N–H…O hydrogen bridge, and anions [Sm(NCS)4(DME)2]–. Sm3+ realizes coordination number eight by four nitrogen atoms of the isothiocyanato ions and by four oxygen atoms of the DME chelates. 1 : Space group P 1, Z = 4, lattice dimensions at 193 K: a = 919.0(1), b = 1965.2(2), c = 2401.3(2) pm, α = 96.748(11)°, β = 94.827(10)°, γ = 91.720(11)°, R = 0.029. 相似文献
67.
Er4F2[Si2O7][SiO4]: The First Rare‐Earth Fluoride Silicate with Two Different Silicate Anions By the reaction of Er2O3 with ErF3 and SiO2 at 700 °C in sealed tantalum capsules using CsCl as flux (molar ratio 5 : 2 : 3 : 20), the compound Er4F2[Si2O7][SiO4] (triclinic, P 1; a = 648.51(5), b = 660.34(5), c = 1324.43(9) pm, α = 87.449(8), β = 85.793(8), γ = 60.816(7)°; Vm = 148.69(1) cm3/mol, Z = 2) is obtained as pale pink platelets or lath‐shaped single crystals. It consists of disilicate anions [Si2O7]6– in eclipsed conformation, ortho‐silicate anions [SiO4]4– and isolated [Er4F2]10+ units comprising two edge‐shared [Er3F] triangles. Er3+ is surrounded by 7 + 1 (Er1) or 7 (Er2–Er4) anionic neighbors, respectively, of which two are F– in the case of Er1 and Er4 but only one for Er2 and Er3. The other ligands recruit from oxygen atoms of the different oxosilicate groups. The crystal structure can be described as simple rowing up of the three building groups ([SiO4]4–, [Er4F2]10+, and [Si2O7]6–) along [001]. The necessity of a large excess of fluoride for a successful synthesis of Er4F2[Si2O7][SiO4] will be discussed. 相似文献
68.
H. F. Kauffmann H. Harms O. F. Olaj 《Journal of polymer science. Part A, Polymer chemistry》1982,20(10):2943-2967
α-Methylstyrene (α-Me-St) in bulk undergoes a variety of thermally induced processes which we investigated in detail by product-distribution analysis. The oligomeric products, shown by GC–MS coupling techniques and independent syntheses, consisted of nine dimers and nine trimers with no detectable higher oligomers or polymers. Two isomeric cyclobutanes and one of the open-chain unsaturated dimers were formed by a conventional two-step cycloaddition; a Flory-type diradical was the common intermediate. In contrast to these 2π + 2π products, the majority of the remaining oligomers could not be interpreted on the basis of π-electron interaction between closed shell molecules. Their structures, however, were compatible with a free radical process in which cumyl(MH·) and 1,4-dimethyl-1-phenyl-tetrahydronaphthalene-yl(THN·), which are consecutive products of 4π + 2π and 2π + 2π interactions, respectively, were involved in addition and transfer reactions. Because of the small rate of initiation and the obvious lack of free radical recombination products, a mechanism was suggested in which MH· and THN· radicals react predominantly in a closed sequence of elementary processes and to a rather small extent only by bimolecular free radical termination. Two sorts of stabilization steps, hydrogen transfer to monomer (RnH· + M → Rn + MH·) and hydrogen abstraction from a hypothetical 4π + 2π intermediate I (RnH· + I → RnH2 + THN·), are attributed to the high rates of unsaturated and saturated oligomer formation. 相似文献
69.
Comparison between capillary electrophoresis and ion-chromatography for analysis of inorganic anions
Separation and detection of some selected inorganic anions with capillary electrophoresis are shown. The anions are separated in microbore capillaries (25 m* 0.2 m) and detected with a UV-detector. Results are compared with the method of ion exchange chromatography. In consideration of the most important physical and chemical parameters an easy kind of computer simulation for such electropherograms was developed.To get optimal results of separation and UV-detection in capillary electrophoresis some parameters of the device HPE 100, i.e. loading time in the electrokinetic sample injection mode and the running voltage are varied. The behaviour of absorption in the UV region of the chosen anions as well as the influence of pH values in retention behaviour are investigated. There is a simple way to calculate the electrophoretic mobilities from known retention times. Approximate limits of detection for all anions and for each technique are given. 相似文献
70.
Uwe Harms 《Mikrochimica acta》1992,109(1-4):131-132
Determinations of methylmercury in biological tissues by gas chromatography with electron-capture detection are often disturbed by electron-capturing compounds simultaneously eluting with the organo-mercury compound.Identification and quantification of methylmercury is improved by interfacing the gas chromatograph to the gas cell of a flameless atomic absorption spectrometer. The construction of the transfer line used is described. 相似文献