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1.
Matrix-Investigations on Monomeric Copper(I) Chloride and its Complexes with N2 and PN Ligands. IR Spectroscopic Results and ab-initio Calculation In solid argon the reaction of monomeric CuCl with N2 yields ClCuN2. On the basis of two absorptions in the ir-spectrum and their corresponding isotopic shifts (14/15N) and with the help of a normal coordinate analysis, linearity of the molecule has been deduced. These results are confirmed by large scale ab-initio Calculations (CPF, MP2). Reaction of monomeric CuCl with molecular PN under matrix condition is shown to give rise to new absorptions in the IR spectrum which arev assigned to a linear molecule ClCuNP. 相似文献
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Preparation and Molecular Structures of Oligofunctional Dirhenium Carbonyl Derivatives from Dirhenium Nonacarbonylphosphane Starting with dirheniumdecacarbonyl, one CO-Ligand was eliminated oxidatively and substituted by the labile acetonitrile ligand. As an intermediate eq-Re2(CO)9NCCH3 was received. The reaction of this labilised carbonyl with tris(trimethylsilyl)phosphine and subsequent methanolysis gave ax-Re2(CO)9PH3, which was isolated and characterized for the first time. Photochemical and thermal reaction of ax-Re2(CO)9PH3 led to the new bi- and trinuclear complexes Re2(μ-H)(μ3-PHRe(CO)5)(CO)8, Re2(μ-PH2)2(CO)8 and Re2(μ-H) · (μ-PH2)(CO)8, which were characterized by IR-, 1H- and 31P-NMR spectroscopy. The structures of ax-Re2(CO)9PH3, Re2(μ-H)(μ3-PHRe(CO)5)(CO)8 and Re2(μ-PH2)2(CO)8 were confirmed by single-crystal X-ray analysis. ax-Re2(CO)9PH3 has a very short Re? P bond length of 228(2) pm. 相似文献
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Summary The novel theoretical scheme IMOMM, integrating ab initio and molecular mechanics contributions in a single geometry optimization process, is applied to the structural determination of different [OsO4(NR3)] (NR3 = bulky chiral alkaloid derivative) species closely related to active catalysts for the asymmetric dihydroxylation of olefins. Computed values compare in a satisfactory way with available X-ray data, the relationship between the Os-N distance and the nature of the NR3, ligand being properly reproduced. The computational scheme allows the separate quantification of electronic and steric effects, as well as the identification of the specific steric repulsions responsible for the difference. 相似文献
7.
Lechosław Łomozik Anna Wojciechowska 《Monatshefte für Chemie / Chemical Monthly》1985,116(6-7):719-727
The influence of the solvent and the substituents on the complexing properties of methyl and phenyl glycine derivatives is discussed. On the basis of a computer analysis of potentiometric titration results, the composition and the stability constants of the complexes ofN-methylglycine,N,N-dimethylglycine,N-phenylglycine and phenylglycine with H+ and with Ni(II), Cu(II), Zn(II) were determined. The ligand-metal coordination mode as well as the zwitterion level in percent in ligand/proton systems were determined by spectral analyses and equilibria studies.
Komplexbildung der Methyl- und Phenylglycin-Derivate in ihren Verbindungen mit dem Proton und Ni(II), Cu(II) und Zn(II)
Zusammenfassung Der Einfluß des Lösungsmittels und der Substituenten auf die komplexbildenden Eigenschaften der Methyl- und Phenylglycin-Derivate wird diskutiert. Anhand einer Computer-Analyse von potentiometrischen Daten wurden die Zusammensetzung und die Beständigkeitskonstanten der Komplexe vonN-Methylglycin,N,N-Dimethylglycin,N-Phenylglycin und Phenylglycin mit H+, Ni(II), Cu(II) und Zn(II) festgestellt. Mittels spektroskopischer Methoden und Gleichgewichtstudien wurde der Koordinationstyp des Liganden mit dem Metall festgestellt sowie der Prozentanteil des Zwitterions im Ligand/Proton-System.相似文献
8.
A novel copper molybdate with mixed ligands, [{(Cu·phen)2(tp)}{(Cu·phen·H2O)2(tp)}{Mo4O14}] (phen=1,10-phenanthroline, tp=terephthalate) 1, has been hydrothermally synthesized and structurally characterized. The crystal belongs to monoclinic system, space group P21/c with a=13.1711(7), b=19.6132(10), c=13.6910(7) (A), β=117.6870(10)°, V=3131.8(3)(A)3, Z=2, C64H44Cu4Mo4N8O24, Mr=1946.99, Dc=2.065 g/cm3, F(000)=1920, μ(MoKα) (A) 2.198 mm-1, R=0.0810 and wR=0.2012 for 4233 observed reflections (Ⅰ > 2σ(Ⅰ)). The structural analysis indicates that the title compound contains a discrete tetramolybdate cluster decorated with copper complex fragments and tp ligands bridging the clusters into a wave-like layer. The hydrogen bonding between adjacent layers further extends the compound into a 3-D framework. 相似文献
9.
Nikolina L. Petrova Dimitar S. Todorovsky Veselinka G. Vasileva 《Central European Journal of Chemistry》2005,3(2):263-278
Mn-, LaMn- and LaCaMn-citrates were synthesized at 60–120°C in ethylene glycol medium using chlorides or nitrates as metal
sources. Their composition, IR spectra and thermal decomposition were studied. Equimolar La/Mn ratio has been established
in the complex, prepared from chloride solution with the same initial composition of the metals. In the isolated three-metallic
complex the molar ratio of the metals deviates from the composition in the initial solution. The final products of the heating
of Mn- and mixed-metal LaMn-citrates at 1000°C are phase-homogeneous Mn3O4 (hausmannite) and LaMnO3 respectively. Parasitic phase(s) are observed in LaxCa1−xMnyO3, produced from LaCaMn-citrate. 相似文献
10.
Rolf Meyer Zu Kcker Gerlinde Frenzen Bernhard Neumüller Kurt Dehnicke Jrg Magull 《无机化学与普通化学杂志》1994,620(3):431-437
Syntheses and Crystal Structures of the Phosphaneimine Complexes MCl2(Me3SiNPMe3)2 with M = Zn and Co, and CoCl2(HNPMe3)2 The molecular complexes MCl2(Me3SiNPMe3)2 (M = Zn, Co) have been prepared by the reaction of the dichlorides of zinc and cobalt with Me3SiNPMe3 in CH3CN and CH2Cl2, respectively, whereas the complex CoCl2(HNPMe3)2 has been prepared by the reaction of CoCl2 with NaF in boiling acetonitrile in the presence of Me3SiNPMe3. All complexes were characterized by IR spectroscopy and by crystal structure determinations. The complexes MCl2(Me3SiNPMe3)2 crystallize isotypically. ZnCl2(Me3SiNPMe3)2: Space group P212121, Z = 4, 2677 observed unique reflections, R = 0.024. Lattice dimensions at ?70°C: a = 1243.6; b = 1319.0; c = 1464.7 pm. CoCl2(Me3SiNPMe3)2: Space group P212121, Z = 4, 3963 observed unique reflections, R = 0,071. Lattice dimensions at ?80°C: a = 1236.3; b = 1317.4; c = 1457.6 pm. CoCl2(HNPMe3)2 · CH2Cl2: Space group Pbca, Z = 8, 1354 observed unique reflections, R = 0.055. Lattice dimensions at ?80°C: a = 1247.3; b = 998.4; c = 2882.4 pm. All complexes have monomeric molecular structures, in which the metal atoms are coordinated in a distorted tetrahedral fashion by the two chlorine atoms and by the nitrogen atoms of the phosphaneimine molecules. 相似文献