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Steve Tisserand Célia Billaud J.R. Falck Charles Mioskowski 《Tetrahedron letters》2006,47(29):5177-5180
CrCl2-mediated condensation of γ-chloro-gem-trichloroalkanes with aldehyde generates homoallylic alcohols through a hydride rearrangement followed by a Nozaki-Hiyama allylation. 相似文献
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Anna M. Maj Albert Demonceau Alfred F. Noels 《Journal of organometallic chemistry》2007,692(14):3048-3056
A range of new imidazolium and imidazolinium chlorides bearing biphenyl units on their nitrogen atoms was synthesized. They differed by the electron-withdrawing or -donating nature and the steric bulk of the substituents on their aromatic rings. These various N-heterocyclic carbene (NHC) precursors were combined with the [RuCl2(p-cymene)]2 dimer and potassium tert-butoxide to generate the corresponding ruthenium-arene complexes [RuCl2(p-cymene)(NHC)] in situ. The catalytic activity of these species was investigated in the photoinduced ring-opening metathesis polymerization (ROMP) of cyclooctene. The results obtained confirmed the necessity of blocking the ortho-positions of the phenyl rings in the vicinity of the metal center in order to attain high catalytic efficiencies. They also showed that changing the steric and electronic properties of the substituents on the remote phenyl rings of the biphenyl units had no significant influence on the outcome of the polymerization. 相似文献
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Rüdiger Beckhaus 《Angewandte Chemie (International ed. in English)》1997,36(7):686-713
The relation of thermodynamic stability and kinetic lability of σ-organometallic compounds of transition metals, together with an improved understanding of the subtle interactions between central metal, ligands, and substrates, has increased the chemist's ability to plan organometallic syntheses. This article presents new results on intermediary and isolable synthetic building blocks incorporating metal–ligand multiple bonds of electron-deficient transition metals; the main emphasis will be placed on compounds with titanium–carbon double bonds. This particular class of compounds is mainly generated by H-transfer reactions starting from readily accessible alkyl and alkenyl derivatives. The preparative use of [L2Ti(CHR2)R′] derivatives as sources for [L2Ti?CR2] intermediates will be discussed, as well as the nature of these intermediates. Application of the same approach to vinyltitanium compounds [L2Ti(CH?CH2)R] opens up an access to a short-lived metallaallene derivative [L2Ti?C?CH2] of an electron-deficient transition metal. The reactivity of these synthetic building blocks is mainly characterized by the nucleophilic properties of the α-C atoms as well as by the spatial orientation of the π-bonding planes. Numerous cycloaddition products with unsaturated substrates could be isolated and characterized for the first time by using [L2Ti?C?CH2] intermediates. Hence it is possible to compare the properties of a multitude of metallacyclic ring systems with those obtained from “Tebbe–Grubbs chemistry”, and in this context, the dependence of the properties of metallacyclic four-membered rings on the substitution pattern is discussed. This class of compounds includes the metallaoxetanes, which have been obtained for the first time by the cycloaddition of the [CpTi?C?CH2] intermediate with cumulenes and metal carbonyls. The differing cycloreversion behavior of these metallaoxetanes enables the differentiation of species exhibiting classical and nonclassical reactivity. The number and position of the exocyclic double bonds are the determining factors of the reactivity of the formed metallacycles. The discussion of the products obtained from titanium methylene and vinylidene building blocks is an up-to-date report on the formation and applications of carbene complexes and carbene intermediates of group 4 metals. 相似文献
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Tungsten(0) carbene complexes of the type (OC)5WC(NMeCH2CHCHCH2OH)R 2 (R=Me: 2a; R=Ph: 2b) were generated by aminolysis of (OC)5WC(OMe)R with cis-NHMeCH2CHCHCH2OH. Like their Cr-congeners 1, complexes 2 exist at room temperature as mixtures of Z- and E-isomers with regard to the C-N bond. The metallacyclic complexes (OC)4WC(η2-NMeCH2CHCHCH2OH)R (4) were obtained in good yields upon photo-decarbonylation of 2. Deprotonation/silylation of the complexes (OC)4MC(η2-NMeCH2CHCHCH2OH)Me (M=Cr: 3a; M=W: 4a) with one equivalent of nBuLi/Me3SiCl gave (OC)4MC(η2-NMeCH2CHCHCH2OSiMe3)CH3 (M=Cr: 5; M=W: 6), whereas with two equivalents of nBuLi/Me3SiCl complexes (OC)4MC(η2-NMeCH2CHCHCH2OSiMe3)CH2SiMe3 (M=Cr: 7; M=W: 8) were formed. Hydrolysis of the latter yielded selectively (OC)4MC(η2-NMeCH2CHCHCH2OH)CH2SiMe3 (M=Cr: 9; M=W: 10). The complexes 1-10 were analyzed in solution by one- and two-dimensional NMR spectroscopy (1H, 13C, 29Si, 1H/1H COSY, 1H/1H NOESY, 13C/1H HETCOR). 相似文献