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Peter Jutzi Andreas Klipp Andreas Mix Beate Neumann Hans-Georg Stammler 《Silicon Chemistry》2007,3(3-4):151-156
Reaction of pentamethylcyclopentadienyl(pentachloro)disilane (2), prepared from hexachlorodisilane and potassium pentamethylcyclopentadienide
(Cp*K), with a further equivalent of Cp*K leads selectively to the title compound Cp*
2
Si
2
Cl
4 (3) which was characterized by NMR and X-ray structural data. Dehalogenation of 3 with four equivalents of sodium naphthalenide
offers an alternative route for the synthesis of decamethylsilicocene (1).
Dedicated to Professor Mitsuo Kira on the occasion of being honoured with the Wacker Silicon Award 2005. 相似文献
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Stasch A Ferbinteanu M Prust J Zheng W Cimpoesu F Roesky HW Magull J Schmidt HG Noltemeyer M 《Journal of the American Chemical Society》2002,124(19):5441-5448
The reaction of the acetylene RC triple bond CH (R = Ph, CH(2)SiMe(3)) with an excess of AlH(3).NMe(3) in boiling toluene leads to the carbaalane [(AlH)(6)(AlNMe(3))(2)(CCH(2)R)(6)] (R = Ph 1, CH(2)SiMe(3) 2) in good yield. Treatment of 2 with BCl(3) under varying conditions gives the chlorinated products [(AlCl)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] 3 and [(AlCl)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(2)Cl)(6)] 4, respectively. The latter clearly demonstrates that the cluster can be stepwise functionalized within the inner and outer sphere. The X-ray single-crystal structures of 1, 2, and 4 have been determined. All compounds have in common that the central core consists of a cluster having eight aluminum and six carbon atoms. The bonding properties in this cluster are described as a new manifestation of three-dimensional surface aromaticity. Each Al(4)C fragment of the cube is formed by four bonds with three electron pairs, thus leading to a strong delocalization of the electrons. A phenomenological modeling using a three-dimensional Hückel scheme with fitted parameters to reproduce the energies from ab initio calculations revealed that the orbital scheme localized at one Al(4)C fragment possesses an orbital sextet with a large HOMO-LUMO gap. This is in line with the criteria of aromaticity. The idea of aromaticity was sustained also by qualitative valence bond reasons enumerating the different resonance structures by means of graph theoretical methods. 相似文献
6.
An approach based on on-line coupled liquid chromatography-gas chromatography (LC-GC) was developed for the rapid analysis of gamma-oryzanol in rice. Total lipids were extracted from rice and subjected to LC-GC without any prior purification. gamma-Oryzanol was pre-separated by HPLC from rice lipids and transferred on-line to GC analysis in order to separate its major constituents. 24-methylenecycloartanyl ferulate, cycloartenyl ferulate, campesteryl ferulate, beta-sitosteryl ferulate and campestanyl ferulate. The identities of the compounds were confirmed by off-line GC-MS analysis. Total gamma-oryzanol content could be quantified by HPLC-UV detection and the distribution of gamma-oryzanol constituents could be determined by on-line coupled GC analysis. The proposed methodology paves the way for high-throughput investigations providing information on natural variations in gamma-oryzanol content and its composition in different rice varieties. 相似文献
7.
Winfried Mientus Hans-Georg Bartel Werner Haberditzl Hans-Joachim Spitzer 《Monatshefte für Chemie / Chemical Monthly》1980,111(3):597-606
A normalization of the wave functions by means of the theoretical exact Multiple-Scattering-(MS)-formalism is discussed within the framework of the SCF-X-SW-method. For the atomic and extramolecular regions the integrals of normalization can be easily determined and the results can be described by the corresponding electronic charges. The calculation of the integral of the interatomic region is problematic. The needful volume integration is only necessary to theGreen's functions of the wave functions and can be solved by means of the residual theory. The further analytical calculation of the surface integrals leads to a complicated formalism which can be numerically evaluated. 相似文献
8.
Petra Hoffman Siegfried Hünig Leonhard Walz Karl Peters Hans-Georg von Schnering 《Tetrahedron》1995,51(48):13197-13216
Azo compounds 1 and 3 containing a CC-double bond in a parallel but distant position are quatemized by Me3OBF4 to 1,MeBF4 and 3,MeBF4, whereas MeI produces the cage compounds 2,HX and 4,HX. These [3+2] cycloadducts also are quantitatively formed from 1,MeBF4 and 3,MeBF4 with catalytic amounts of azo compounds. Intermolecular [3+2] cycloadditions occur with a mixture of DBH (5) or DBO (8), MeI and a variety of alkenes (→ HI) salts of (6, 7, 9 — 12). The intermediate azomethineimines, if stabilized by a fluorenylidene group, can be isolated (20, 22,24), but not, however, in the presence of a close parallel CC-bond (25 → 26). 相似文献
9.
Schiefer M Reddy ND Ahn HJ Stasch A Roesky HW Schlicker AC Schmidt HG Noltemeyer M Vidovic D 《Inorganic chemistry》2003,42(16):4970-4976
The syntheses of the ionic compounds [Li(+).2 dioxane (2,6-iPr(2)C(6)H(3)N(SiMe(3))Al(C triplebond CSiMe(3))(3))(-)].0.75 dioxane (1), [(Li(+))(2).(dioxane)(7)](0.5) [2,6-iPr(2)C(6)H(3)N(SiMe(3))Ga(C triplebond CSiMe(3))(3)(-)].1.5 dioxane (2), and [(Li(+))(2).(dioxane)(7)](0.5) [2,6-iPr(2)C(6)H(3)N(SiMe(3))In(C triplebond CSiMe(3))(3)(-)].1.5 dioxane (3) by the reaction of the corresponding organo metal chloride with LiC triplebond CSiMe(3) are reported. The neutral ethynyl compounds Br-Al(C triplebond CtBu)(2).2 THF (4), Cl-Ga(C triplebond CtBu)(2).THF (5), Cl-In(C triplebond CtBu)(2).2 THF (6), Al(C triplebond CtBu)(3).C[N(Me)CMe](2) (7), Ga(C triplebond CtBu)(3).dioxane (8), and In(C triplebond CtBu)(3).NEt(3) (9) have been obtained in good yields from the reaction of AlBr(3), GaCl(3), and InCl(3) with LiC triplebond CtBu in the presence of a Lewis base. Compound 7 is the first heterocyclic carbene substituted ethynyl derivative. Aluminum and gallium compounds with three terminal ethynyl groups Al(C triplebond CPh)(3).NMe(3) (10) and Ga(C triplebond CPh)(3).NMe(3) (11) have been prepared by the reaction of AlH(3).NMe(3) or GaH(3).NMe(3) with three equivalents of phenylethyne. All the above-mentioned compounds have been structurally studied. In compound 1 the lithium ion is coordinated to the three terminal ethynyl groups, whereas in compounds 2 and 3 the lithium is coordinated to the solvent (dioxane). Compound 8 crystallizes as a coordination polymer with dioxane molecules bridging the individual gallium units. 相似文献
10.
Stasch A Roesky HW Vidovic D Magull J Schmidt HG Noltemeyer M 《Inorganic chemistry》2004,43(12):3625-3630
The carbaalane halogen derivatives [(AlX)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (X = F (9), Cl (7), Br (10), I (11)) were prepared in toluene from [(AlH)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (6) and BF(3).OEt(2), BX(3) (X = Br, I), Me(3)SnF, and Me(3)SiX (X = Cl, Br, I), respectively. A partially halogenated product [(AlH)(2)(AlX)(4)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (12) (X = Cl (approximately 40%), Br (approximately 60%)) was obtained from 5 and impure BBr(3). [(AlH)(6)(AlNMe(3))(2)(CCH(2)Ph)(6)] (5) was converted to [(AlX)(6)(AlNMe(3))(2)(CCH(2)Ph)(6)] (X = F (13), Cl (14), Br (15), I (16)) using BF(3).OEt(2) and Me(3)SiX (X = Cl, Br, I), respectively. The X-ray single-crystal structures of 11.C(6)H(6), 12.3C(7)H(8), 13.6C(7)H(8), and 15.4C(7)H(8) were determined. Compounds 7 and 9-11 are soluble in benzene/toluene and could be well characterized by NMR spectroscopy and MS (EI) spectrometry. The results demonstrate the facile substitution of the hydridic hydrogen atoms in 5 and 6 by the halides with different reagents. 相似文献