全文获取类型
收费全文 | 13175篇 |
免费 | 627篇 |
国内免费 | 809篇 |
专业分类
化学 | 13695篇 |
晶体学 | 142篇 |
力学 | 9篇 |
综合类 | 29篇 |
数学 | 152篇 |
物理学 | 584篇 |
出版年
2023年 | 99篇 |
2022年 | 265篇 |
2021年 | 304篇 |
2020年 | 430篇 |
2019年 | 356篇 |
2018年 | 299篇 |
2017年 | 293篇 |
2016年 | 382篇 |
2015年 | 270篇 |
2014年 | 362篇 |
2013年 | 797篇 |
2012年 | 1350篇 |
2011年 | 523篇 |
2010年 | 466篇 |
2009年 | 641篇 |
2008年 | 716篇 |
2007年 | 869篇 |
2006年 | 666篇 |
2005年 | 626篇 |
2004年 | 610篇 |
2003年 | 518篇 |
2002年 | 418篇 |
2001年 | 363篇 |
2000年 | 358篇 |
1999年 | 339篇 |
1998年 | 293篇 |
1997年 | 289篇 |
1996年 | 312篇 |
1995年 | 313篇 |
1994年 | 213篇 |
1993年 | 185篇 |
1992年 | 154篇 |
1991年 | 104篇 |
1990年 | 62篇 |
1989年 | 50篇 |
1988年 | 51篇 |
1987年 | 42篇 |
1986年 | 37篇 |
1985年 | 29篇 |
1984年 | 31篇 |
1983年 | 12篇 |
1982年 | 27篇 |
1981年 | 14篇 |
1980年 | 20篇 |
1979年 | 13篇 |
1978年 | 7篇 |
1977年 | 7篇 |
1975年 | 5篇 |
1974年 | 3篇 |
1973年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
Prochiral alkenes, aldehydes, and ketones constitute the most frequently used starting materials for enantioselective organic syntheses. Protocols often involve chiral binding agents or Lewis acids that can give two diastereomeric adducts, the ratios of which are measures of chiral recognition. With π adducts, the diastereomers differ in the enantioface of the C?C or O?C group bound to the Lewis acid. This review provides the first comprehensive analysis of such equilibria and related binding phenomena with chiral transition metal Lewis acids. An extensive body of data from the authors' laboratory for complexes of the pyramidal rhenium fragment [(η5?C5H5)Re(No)(PPh3)]+ ( I ) affords particular insight. Literature data for other complexes are also summarized. A general model for chiral recognition based upon the relative steric properties of four quadrants is presented. This enables binding selectivities to be individually and rationally optimized for different classes of ligands. Electronic effects are also identified and correlated with specific structural properties. Relationships between binding equilibria, reactivity, and product configurations are discussed. 相似文献
72.
L. F. Kosyanchuk N. V. Kozak O. I. Antonenko G. Ya. Menzheres Yu. S. Lipatov 《Theoretical and Experimental Chemistry》2006,42(6):357-363
For semi-interpenetrating polymer networks (semi-IPNs) based on an incompatible polyurethane network/linear polymethylmethacrylate
pair formed in situ in the presence of 3d metal chelates, we have studied the effect of the system composition on the kinetics
of formation of the components and the nature of complex formation between the metal compound and the polymer matrix. The
ratio of the system components has been shown to have an effect on the selection of the macroligand in formation of complexes
of the metal chelate with the polar groups of the semi-IPN, where the general character of the kinetic behavior for the formation
of the network and the linear polymer is preserved.
__________
Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 6, pp. 351–356, November–December, 2006. 相似文献
73.
Unusual Formation and Structure of a O‐Sulfinato Zinc Complex Whereas the reaction between hydrotris[(N‐xylyl)‐thioimidazolyl]borato‐zinc perchlorate ([ L· Zn‐OClO3]) and ethanethiolate under an inert atmosphere leads to the thiolate complex [ L· Zn‐SC2H5], the same reaction in air produces the sulfinato complex [ L· Zn‐O‐S(O)‐C2H5] ( 1 ). 1 is the first fully characterized sulfinato‐zinc complex. Its structure determination has confirmed the unusual coordination of the sulfinato ligand via one of its oxygen atoms. 相似文献
74.
低氧条件下,钴(Ⅲ)的氮芥配合物具有合适的还原电位,就可能还原得到比较活泼的Co(Ⅱ)配合物,在溶液中其活性配体很快被体内的小分子取代,释放出的活性配体可以杀死低氧区内外的癌细胞,因此筛选合适的钴配合物作为低氧选择性抗癌药物的研究很有意义。本文以双 (2 氯乙基)胺(简称BCA)为活性配体,取代乙酰丙酮为辅助配体,合成一系列Co(Ⅲ)配合物(下图)。初步评估结果表明,其中两个配合物具有一定的低氧选择性,配合物的还原电位对药物的低氧选择性影响很大,合适的还原范围可能比较窄。1 实验部分1.1 试剂与仪器按文献[1]的方法合成… 相似文献
75.
[Co(amp)2Cl2]2[ZnCl4]体系中两对称异构体的2D NMR研究 总被引:7,自引:0,他引:7
The two symmetrical isomers in [Co(amp)2Cl2]2[ZnCl4](amp=2-(Aminomethyl)pyridine) system were syn-thesized by general oxidation method and were separated by chromatography and recrystallization method. Their configurations were assigned by using 2D NMR techniques, particularly the NOESY NMR spectra. Solvent used was Me2SO-d6 with the central peak of the CD3 septet as the reference ( 13C,δ 39.37; 1H,δ 2.49 relative to SiMe4). Cation exchange media used was Dowex 50Wx 2(H+ form, 200~400mesh; Biorad). 相似文献
76.
Polynuclear Complexes with Fe? As, Fe? Sb, and Fe? Bi Frameworks The anionic iron clusters Fe3(CO)112? and Fe4(CO)132? were reacted with compounds EX3 and with organic derivatives REX2 and R2EX of the elements arsenic, antimony, and bismuth. Commonly redox and cluster degradation reactions were observed. The new complexes [(CO)4Fe? AsMe2? Fe(CO)4]?, [HFe3(CO)9(mu;3-SbBut)]?, [Fe3(CO)10 (mu;3-Sb)]?, and [Fe3(CO)10(mu;3-Bi)]? were formed and isolated as their PPN salts. The Fe? As? Fe complex was identified by a structure determination, the other complexes were identified by their spectra. 相似文献
77.
78.
Yoshihiko Nishimori Katsuhiko Kanaizuka Dr. Masaki Murata Dr. Hiroshi Nishihara Prof. 《化学:亚洲杂志》2007,2(3):367-376
Films of linear and branched oligomer wires of Fe(tpy)2 (tpy=2,2′:6′,2′′‐terpyridine) were constructed on a gold‐electrode surface by the interfacial stepwise coordination method, in which a surface‐anchoring ligand, (tpy? C6H4N?NC6H4? S)2 ( 1 ), two bridging ligands, 1,4‐(tpy)2C6H4 ( 3 ) and 1,3,5‐(C?C? tpy)3C6H3 ( 4 ), and metal ions were used. The quantitative complexation of the ligands and FeII ions was monitored by electrochemical measurements in up to eight complexation cycles for linear oligomers of 3 and in up to four cycles for branched oligomers of 4 . STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots of uniform size and shape, which suggests the quantitative formation of dendritic structures. The electron‐transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential‐step chronoamperometry (PSCA). The unique current‐versus‐time behavior observed under all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. Redox conduction in a single molecular wire in a redox‐polymer film has not been reported previously. The analysis provided the rate constant for electron transfer between the electrode and the nearest redox‐complex moiety, k1 (s?1), as well as that for intrawire electron transfer between neighboring redox‐complex moieties, k2 (cm2 mol?1 s?1). The strong effect of the electrolyte concentration on both k1 and k2 indicates that the counterion motion limits the electron‐hopping rate at lower electrolyte concentrations. Analysis of the dependence of k1 and k2 on the potential gave intrinsic kinetic parameters without overpotential effects: k10=110 s?1, k20=2.6×1012 cm2 mol?1 s?1 for [n Fe 3 ], and k10=100 s?1, k20=4.1×1011 cm2 mol?1 s?1 for [n Fe 4 ] (n=number of complexation cycles). 相似文献
79.
Fadila Balegroune Pierre Braunstein Laurent Douce Yves Dusausoy Daniel Grandjean Michael Knorr Martin Strampfer 《Journal of Cluster Science》1992,3(3):275-296
The reactions of K[Fe{Si(OMe)3}(CO)3(PY)][PY=Ph2PCH2C(O)Ph, Ph2PCH2C(O)[(-C5H4)FeCp] (Cp=5-C5H5), Ph2P(CH2)2CN] with CdCl2·2.5H2O, ZnX
2 (X=Cl, I) or InCl3 afforded Fe-Cd-Fe or Fe-M(-X)2
M-Fe (M=Cd, Zn, In;X=Cl, I) and Fe-InCl2 complexes. Some of them contain an unusual and labile -2-SiO alkoxysilyl bridge which may be associated with a bridging mode for the ketophosphine ligand (first such example structurally established), thus providing original results in bimetallic chemistry on the intramolecular coordination of oxygendonor functions ofchemically different hemilabile ligands firmly attached to a neighboring metal center. The structures of the trinuclear complex (3), of the chlorobenzene solvate of the tetranuclear complex (4a·C6H5Cl) and of [mer-(OC)3{(EtO)3Si} (4e) have been determined by X-ray diffraction. Crystals of 3 are orthorhombic, space groupPbcn, witha=19.010(4),b=11.766(5),c=26.998(7)Å, andZ=4. Crystals of4a·C6H5Cl are monoclinic, space groupC2/c witha=22.455(3),b=17.680(2),c=16.627(4)Å, =90.80(4)°, andZ=4. Crystals of4e are monoclinic, space groupC2/c witha=25.392(5),b=18.554(6),c=16.28(1)Å, =120.73(3)°, andZ=4. The structures were solved using direct methods and Fourier difference techniques and refined by blocked full-matrix least squares toR=0.035 (R
w
=0.049) for 2719 observed reflections, toR=0.042 (R
w
=0.056) for 3082 observed reflections, and toR=0.057 (R
w
=0.075) for 1850 observed reflections for3, 4a·C6H5Cl and4e, respectively. The Fe-Zn complexes (9a), (9b) and (9c) were prepared and characterized by spectroscopic methods.Part 21 in the Series: Complexes with Functional Phosphines. Part 20: P. Braunstein, S. Coco Cea, A. DeCian, and J. Fischer (1992).Inorg. Chem.
31, 4203. 相似文献
80.
通过由Fe3(CO)12、RSH和Et3N所形成的[(μ-CO)(μ-RS)Fe2(CO)6]Et3NH于室温下分别与对或间苯二甲酰氯的原位反应,首次合成6个结构新颖的苯二甲酰基桥联铁硫配合物[(μ-RS)·Fe2(CO)6]2(μ-p-OCC6H4CO-p-μ)(R=Et,n-Bu,t-Bu)以及[(μ-RS)Fe2(CO)6]2(μ-m-OCC6H4CO-m-μ)(R=n-Pr,n-Bu,t-Bu)。经元素分析、IR光谱及1HNMR表征了它们的结构,并讨论了产物的生成过程。此外,还提出了合成对苯二甲酰氯的一种新方法。 相似文献