全文获取类型
收费全文 | 356篇 |
免费 | 16篇 |
专业分类
化学 | 304篇 |
力学 | 3篇 |
数学 | 10篇 |
物理学 | 55篇 |
出版年
2021年 | 3篇 |
2019年 | 12篇 |
2018年 | 5篇 |
2016年 | 9篇 |
2015年 | 5篇 |
2014年 | 8篇 |
2013年 | 11篇 |
2012年 | 17篇 |
2011年 | 17篇 |
2010年 | 9篇 |
2009年 | 8篇 |
2008年 | 10篇 |
2007年 | 4篇 |
2006年 | 10篇 |
2005年 | 12篇 |
2004年 | 12篇 |
2003年 | 4篇 |
2002年 | 10篇 |
2001年 | 11篇 |
2000年 | 12篇 |
1999年 | 13篇 |
1998年 | 15篇 |
1997年 | 6篇 |
1996年 | 6篇 |
1995年 | 7篇 |
1994年 | 9篇 |
1993年 | 12篇 |
1992年 | 15篇 |
1991年 | 11篇 |
1990年 | 6篇 |
1989年 | 12篇 |
1988年 | 7篇 |
1987年 | 5篇 |
1986年 | 11篇 |
1985年 | 7篇 |
1982年 | 3篇 |
1980年 | 5篇 |
1979年 | 2篇 |
1978年 | 6篇 |
1977年 | 4篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 2篇 |
1971年 | 1篇 |
1958年 | 1篇 |
1943年 | 1篇 |
1937年 | 2篇 |
1936年 | 4篇 |
排序方式: 共有372条查询结果,搜索用时 15 毫秒
361.
362.
363.
Phosphoraneiminato Complexes of Bismuth(III). Crystal Structures of [BiF2(NPEt3)(HNPEt3)]2 and [Bi2I(NPPh3)4]I3 [BiF2(NPEt3)(HNPEt3)]2 ( 1 ) has been obtained by the reaction of BiF3 with Me3SiNPEt3 at 100 °C and subsequent extraction with 1,2‐dimethoxyethane in the presence of traces of water forming pale‐yellow, moisture sensitive crystals, which were characterized by a crystal structure determination. Space group P21/n, Z = 4, lattice dimensions at –83 °C: a = 2105.0, b = 1195.8, c = 728.2 pm, β = 92.55°. 1 forms centrosymmetric dimeric molecules, in which the Bi atoms are linked via Bi–N bonds of varying length (213.9 and 240.1 pm) of the NPEt3– groups to form a Bi2N2 four‐membered ring. The longer one of the two Bi–N bonds is trans to one terminal F atom. [Bi2I(NPPh3)4]I3 ( 2 ) has been obtained by the reaction of bismuth with N‐iodine triphenylphosphaneimine in dichloromethane forming red crystals. Crystal structure determination of 2 · 2.5 CH2Cl2: Space group P21/n, Z = 4, lattice dimensions at –50 °C: a = 1542.6, b = 2409.1, c = 2173.5 pm, β = 105.82°. In 2 the Bi atoms are linked via two N atoms of two NPPh3– groups to form a non‐planar Bi2N2 four‐membered ring with a fold angle of 27° along the N…N connection line. The two remaining NPPh3– groups are terminally connected and bent in the same direction. The iodide ion caps the two Bi atoms so that a [Bi2I(NPPh3)4]+ cation is formed. 相似文献
364.
Gernot Boche Ferdinand Bosold Michael Marsch Klaus Harms 《Angewandte Chemie (International ed. in English)》1998,37(12):1684-1686
Different types of bonding are present in cyanocuprates 1 and 2 , whose crystal structures could be determined (the drawings below show the important structural characteristics). Accordingly, 1 is a lower order cyanocuprate of the type RCu(CN)Li, whereas 2 , which is of the type R2Cu(CN)Li2, does not exist as a “higher order” cyanocuprate with Cu–CN bonds, but rather as a cyano-Gilman cuprate. 相似文献
365.
Andreas Mommertz Roland Leo Werner Massa Klaus Harms Kurt Dehnicke 《无机化学与普通化学杂志》1998,624(10):1647-1652
Synthesis of a Titana-Oxacyclohexane Ring by Controlled Ring Opening of Tetrahydrofurane. Crystal Structures of [Ti(CH2)4O{Me2Si(NBut)2}]2, [TiCl{Me2Si(NBut)2}]3(μ3-O)(μ3-Cl), and [Li2(THF)3{Me2Si(NBut)2}] [TiCl3(THF)3] reacts with [(ButNLi)2SiMe2]2 in diethyl ether at –35 °C under redox disproportionation and formation of the yellow titana(IV)-oxacyclohexane complex [Ti(CH2)4O{Me2Si(NBut)2}]2. According to the crystal structure analysis the titanium atoms are linked to form centrosymmetric dimers via the oxygen atoms of the Ti(CH2)4O six-membered rings, which are in chair conformation. Along with the nitrogen atoms of the chelating [Me2Si(NBut)2]2– ligands the titanium atoms obtain a distorted trigonal-bipyramidal surrounding. While [TiCl{Me2Si(NBut)2}]3(μ3-O)(μ3-Cl) with a cluster-like structure is obtained as a by-product. According to the crystal structure analysis of [Li2(THF)3 · {Me2Si(NBut)2}], which is involved in the synthesis reaction, the two lithium atoms are connected with both the nitrogen atoms of the t-butyl amide groups and bridged via an oxygen atom of one of the THF molecules. 相似文献
366.
Synthesis and Crystal Structures of the Phosphaneimine Complexes [Cu(μ-HNPEt3)]4(O3S–CF3)4 and [Pt2Me6(μ-I)2(μ-HNPMe3)] The title compounds have been prepared by the reaction of copper(I)triflate with [NiBr(NPEt3)]4 in CH2Cl2 suspension in the presence of water, and by the reaction of [PtMe3I]4 with Me3SiNPMe3 in boiling toluene in the presence of cesium fluoride, respectively. According to the crystal structure determinations the cation of the copper complex forms tetrameric units [Cu(HNPEt3)]44+ with S4 symmetry with Cu–N bond lengths of 191.6 and 192.1 pm. In the platinum complex the platinum atoms are linked by two μ-I bridging atoms as well as by the μ-N atom of the HNPMe3 ligand with Pt–N bond lengths of 228.1 and 229.5 pm. 相似文献
367.
Phosphoraneiminato Complexes of Zinc with Hydrido, Alkynylo, Alkenylo, and Amido Ligands Synthesis and properties of the phosphoraneiminato complexes [ZnCl(NPMe3)]4 ( 1 ), [ZnH(NPMe3)]4 ( 2 ) as well as of the alkynylo derivatives [Zn(C≡C–SiMe3)(NPMe3)]4 ( 3 ), [Zn(C≡C–C≡C–SiMe3)(NPR3)]4 [R = Me ( 4 a ), R = Et ( 4 b )], [Zn(C≡C–Ph)(NPMe3)]4 ( 5 ) and of the alkenylozinc complexes [Zn(CH=CHMe)(NPR3)]4 [R = Me ( 6 a ), R = Et ( 6 b )] are described. According to crystal structure analyses of 1 , 3 , and 4 b these complexes possess heterocubane structures with only slightly distorted Zn4N4 cubic skeletons. Experiments to substitute the terminal ligands at the zinc atoms by bis(trimethylsilyl)amido groups lead to disintegration of the heterocubanes and formation of the dimeric complex [Zn(μ2-NPEt3){N(SiMe3)2}]2 ( 7 ) and of the trinuclear derivative [Zn3(μ2-NPMe3)4{N(SiMe3)2}2] ( 8 ), in which the central zinc atom is surrounded by the four N atoms of the NPEt3– groups in a spiro-cyclic fashion. 7 and 8 are also characterized by crystal structure analyses. 相似文献
368.
Matthias Krieger Gertraud Geiseler Klaus Harms Jan Merle Werner Massa Kurt Dehnicke 《无机化学与普通化学杂志》1998,624(9):1387-1388
Crystal Structures of the Triarylzincates [Mg2Br3(THF)6][ZnPh3] and [MgBr(THF)5][ZnMes3] The title compounds were obtained from reactions of the phosphoraneiminato complex [ZnBr(NPMe3)]4 with excess Grignard reagents RMgBr (R = C6H5, 2,4,6-(CH3)3–C6H2) in THF solution. According to X-ray structure determinations the [ZnR3]– ions contain zinc atoms which are coordinated in a planar fashion with Zn–C distances of 200.7 pm (R = Ph) and 203.4 pm (R = Mes) in average. 相似文献
369.
The Reactions of Europium and Yttrium with N‐Iodinetriphenylphosphoraneimine. Crystal Structures of [EuI2(DME)3], [Eu2I(NPPh3)5(DME)] and [Y2I(NPPh3)4(THF)4]+I3– When treated with ultrasound, the reaction of europium metal with INPPh3 in 1,2‐dimethoxyethane (DME) leads to the complexes [EuI2(DME)3] ( 1 ) and [Eu2I(NPPh3)5(DME)] ( 2 ) which are separated from each other by fractional crystallization. On the other hand, the reaction of yttrium metal with INPPh3 under similar conditions in THF gives the ionic phosphoraneiminato complex [Y2I(NPPh3)4(THF)4]+I3– ( 3 ). All complexes are characterized by crystal structure determinations. 1 : Space group P21, Z = 2, lattice dimensions at 188 K: a = 848.9(1); b = 1059.4(1); c = 1227.9(1) pm; β = 93.793(6)°; R = 0.0246. In the molecular structure of 1 the europium atom is eightfold coordinated with a bond angle I–Eu–I of 158.51°. 2 · 2 DME: Space group P1, Z = 2, lattice dimensions at 193 K: a = 1405.5(1); b = 1652.2(2); c = 2203.7(2) pm; α = 89.404(11)°; β = 72.958(11)°; γ = 78.657(11)°; R = 0.0391. In 2 the europium atoms are linked by the μ‐N‐atoms of two (NPPh3–) groups to form a planar Eu2N2 four‐membered ring. One of the Eu atoms is terminally coordinated by the N atoms of two (NPPh3–) groups, thus achieving a distorted tetrahedral surrounding. The second Eu atom is coordinated by the N atom of one (NPPh3–) group, by the terminally bounded iodine atom and by the oxygen atoms of the DME chelate, thus achieving a distorted octahedral surrounding. 3 · 61/2 THF: Space group P1, Z = 2, lattice dimensions at 103 K: a = 1739.7(2); b = 1770.1(2); c = 2153.8(3) pm; α = 74.929(15)°; β = 84.223(14)°; γ = 64.612(12)°; R = 0.0638. In the cation [Y2I(NPPh3)4(THF)4]+ of 3 the yttrium atoms are linked by the μ‐N atoms of two (NPPh3–) groups as well as by the μ‐I atom. One (NPPh3–) ligand and two THF molecules complete the distorted octahedral coordination at each yttrium atom. 相似文献
370.