全文获取类型
收费全文 | 722篇 |
免费 | 30篇 |
国内免费 | 1篇 |
专业分类
化学 | 548篇 |
晶体学 | 14篇 |
力学 | 4篇 |
数学 | 40篇 |
物理学 | 147篇 |
出版年
2023年 | 6篇 |
2022年 | 2篇 |
2021年 | 8篇 |
2020年 | 21篇 |
2019年 | 13篇 |
2018年 | 15篇 |
2017年 | 5篇 |
2016年 | 15篇 |
2015年 | 18篇 |
2014年 | 21篇 |
2013年 | 36篇 |
2012年 | 44篇 |
2011年 | 47篇 |
2010年 | 36篇 |
2009年 | 34篇 |
2008年 | 48篇 |
2007年 | 49篇 |
2006年 | 59篇 |
2005年 | 50篇 |
2004年 | 38篇 |
2003年 | 40篇 |
2002年 | 35篇 |
2001年 | 4篇 |
2000年 | 7篇 |
1999年 | 9篇 |
1998年 | 7篇 |
1997年 | 8篇 |
1995年 | 3篇 |
1994年 | 7篇 |
1993年 | 9篇 |
1992年 | 4篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 5篇 |
1980年 | 4篇 |
1978年 | 2篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
1963年 | 1篇 |
1962年 | 3篇 |
1954年 | 1篇 |
排序方式: 共有753条查询结果,搜索用时 15 毫秒
111.
Arashiba K Iizuka H Matsukawa S Kuwata S Tanabe Y Iwasaki M Ishii Y 《Inorganic chemistry》2008,47(10):4264-4274
The reaction of the group 9 bis(hydrosulfido) complexes [Cp*M(SH)2(PMe3)] (M=Rh, Ir; Cp*=eta(5)-C 5Me5) with the group 6 nitrosyl complexes [Cp*M'Cl2(NO)] (M'=Mo, W) in the presence of NEt3 affords a series of bis(sulfido)-bridged early-late heterobimetallic (ELHB) complexes [Cp*M(PMe3)(mu-S)2M'(NO)Cp*] (2a, M=Rh, M'=Mo; 2b, M=Rh, M'=W; 3a, M=Ir, M'=Mo; 3b, M=Ir, M'=W). Similar reactions of the group 10 bis(hydrosulfido) complexes [M(SH)2(dppe)] (M=Pd, Pt; dppe=Ph 2P(CH2) 2PPh2), [Pt(SH)2(dppp)] (dppp=Ph2P(CH2) 3PPh2), and [M(SH)2(dpmb)] (dpmb=o-C6H4(CH2PPh2)2) give the group 10-group 6 ELHB complexes [(dppe)M(mu-S)2M'(NO)Cp*] (M=Pd, Pt; M'=Mo, W), [(dppp)Pt(mu-S)2M'(NO)Cp*] (6a, M'=Mo; 6b, M'=W), and [(dpmb)M(mu-S)2M'(NO)Cp*] (M=Pd, Pt; M'=Mo, W), respectively. Cyclic voltammetric measurements reveal that these ELHB complexes undergo reversible one-electron oxidation at the group 6 metal center, which is consistent with isolation of the single-electron oxidation products [Cp*M(PMe3)(mu-S)2M'(NO)Cp*][PF6] (M=Rh, Ir; M'=Mo, W). Upon treatment of 2b and 3b with ROTf (R=Me, Et; OTf=OSO 2CF 3), the O atom of the terminal nitrosyl ligand is readily alkylated to form the alkoxyimido complexes such as [Cp*Rh(PMe3)(mu-S)2W(NOMe)Cp*][OTf]. In contrast, methylation of the Rh-, Ir-, and Pt-Mo complexes 2a, 3a, and 6a results in S-methylation, giving the methanethiolato complexes [Cp*M(PMe3)(mu-SMe)(mu-S)Mo(NO)Cp*][BPh 4] (M=Rh, Ir) and [(dppp)Pt(mu-SMe)(mu-S)Mo(NO)Cp*][OTf], respectively. The Pt-W complex 6b undergoes either S- or O-methylation to form a mixture of [(dppp)Pt(mu-SMe)(mu-S)W(NO)Cp*][OTf] and [(dppp)Pt(mu-S) 2W(NOMe)Cp*][OTf]. These observations indicate that O-alkylation and one-electron oxidation of the dinuclear nitrosyl complexes are facilitated by a common effect, i.e., donation of electrons from the group 9 or 10 metal center, where the group 9 metals behave as the more effective electron donor. 相似文献
112.
113.
Barium-catalyzed direct Mannich-type reactions of a beta,gamma-unsaturated ester are described. The Ba-catalyst not only promoted the Mannich-type reactions, but also isomerized Mannich adducts to afford beta-methyl aza-Morita-Baylis-Hillman-type products in 61-88% yield from various aryl, heteroaryl, and alkyl imines. Preliminary trials on enantioselective variants with a chiral biaryldiol ligand gave products in up to 80% ee. 相似文献
114.
Hydrogenation of cyclohexene with 0.1 mol% of the (nitrosyl)ruthenium catalyst [Cp∗Ru(NO)(C6H5)2] (1; Cp∗ = η5-C5(CH3)5) under 1.0 MPa of H2 in water at 90 °C for 13 h afforded cyclohexane in 94% yield. The nitrosyl-bridged dinuclear complex [Cp∗Ru(μ2-NO)2RuCp∗] (2) and the mononuclear cyclohexene complex [Cp∗Ru(NO)(η2-C6H10)] (3), which also serve as catalyst precursors, have been obtained from the reaction mixture. X-ray crystallographic analyses of 2 and 3 have revealed that the bridging nitrosyl ligands in 2 form an almost planar Ru2N2 four-membered ring with the Ru–Ru distance of 2.5366(5) Å, whereas the nitrosyl ligand in 3 is linear. On the other hand, a ruthenium complex without a nitrosyl ligand [Cp∗Ru(CH3CN)3][OSO2CF3] proved to be less effective for this hydrogenation. 相似文献
115.
Hayashi K Kujime E Katayama H Sano S Nagao Y 《Chemical & pharmaceutical bulletin》2007,55(12):1773-1775
In the imine aldol reactions of 1 with aromatic aldehydes using magnesium salts in the presence of amines, the threo/erythro ratios of products increased in the order Mg(ClO4)2>MgI2>MgBr2>MgCl2>Mg(OTf)2 and N,N,N',N'-tetramethylethylenediamine (TMEDA)>Et3N. This increase in the threo/erythro ratios of products was estimated to be caused by a retro-imine aldol reaction under thermodynamic control. 相似文献
116.
Low-frequency infrared (IR) and depolarized Raman scattering (DRS) spectra of acetonitrile, methylene chloride, and acetone liquids are simulated via molecular dynamics calculations with the charge response kernel (CRK) model obtained at the second order M?ller-Plesset perturbation (MP2) level. For this purpose, the analytical second derivative technique for the MP2 energy is employed to evaluate the CRK matrices. The calculated IR spectra reasonably agree with the experiments. In particular, the agreement is excellent for acetone because the present CRK model well reproduces the experimental polarizability in the gas phase. The importance of interaction induced dipole moments in characterizing the spectral shapes is stressed. The DRS spectrum of acetone is mainly discussed because the experimental spectrum is available only for this molecule. The calculated spectrum is close to the experiment. The comparison of the present results with those by the multiple random telegraph model is also made. By decomposing the polarizability anisotropy time correlation function to the contributions from the permanent, induced polarizability and their cross term, a discrepancy from the previous calculations is observed in the sign of permanent-induce cross term contribution. The origin of this discrepancy is discussed by analyzing the correlation functions for acetonitrile. 相似文献
117.
Metalation of meso-hexakis(pentafluorophenyl)-substituted [26]hexaphyrin(1.1.1.1.1.1) (1) has been explored with group 12 metal ions Zn(II), Cd(II), and Hg(II). Zn(II) and Cd(II) ions afforded dinuclear gable-shaped complexes 2 and 3 in good yields, while Hg(II) ion provided bis-Hg(II) and mono-Hg(II) planar complexes (4 and 5) via C-H bond cleavage. 相似文献
118.
119.
The effects of the direction of transition dipole moment on polarization-dependent phase-conjugate (PC) reflectivity by degenerate four-wave mixing in a saturable-dye-doped film are theoretically investigated. On the basis of a four-energy-level model for the saturable dyes, the pump-intensity dependence of the PC reflectivity is calculated for the two cases of a probe wave being polarized either parallel or perpendicular to pump waves, when the transition dipole moment associated with excited-state absorption tilts from that associated with ground-state one. For the parallel polarization, in the case of two transition dipole moments having different directions, a dip appears in the PC reflectivity curve near a resonant frequency on account of the characteristics of nonlinear absorption, whereas it disappears when the frequency of light is off resonance due to the influence of nonlinear refractive index. 相似文献
120.