全文获取类型
收费全文 | 495篇 |
免费 | 27篇 |
专业分类
化学 | 390篇 |
晶体学 | 4篇 |
力学 | 6篇 |
数学 | 45篇 |
物理学 | 77篇 |
出版年
2023年 | 7篇 |
2022年 | 5篇 |
2021年 | 8篇 |
2020年 | 17篇 |
2019年 | 11篇 |
2018年 | 11篇 |
2017年 | 10篇 |
2016年 | 13篇 |
2015年 | 19篇 |
2014年 | 22篇 |
2013年 | 36篇 |
2012年 | 31篇 |
2011年 | 49篇 |
2010年 | 18篇 |
2009年 | 31篇 |
2008年 | 22篇 |
2007年 | 20篇 |
2006年 | 26篇 |
2005年 | 30篇 |
2004年 | 22篇 |
2003年 | 29篇 |
2002年 | 23篇 |
2001年 | 9篇 |
2000年 | 7篇 |
1999年 | 5篇 |
1998年 | 6篇 |
1996年 | 4篇 |
1994年 | 2篇 |
1993年 | 6篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1954年 | 1篇 |
排序方式: 共有522条查询结果,搜索用时 15 毫秒
391.
The compounds, 2,6-bis(3,5-dimethylpyrazol-1-ylmethyl)pyridine (MeNˆNˆN) (L1) and 2,6-bis(3,5-ditertbutylpyrazol-1-ylmethyl)pyridine (tBuNˆNˆN) (L2), react with either [Pd(NCMe)2Cl2] or [Pd(COD)ClMe] to form the mononuclear palladium complexes [Pd(MeNˆNˆN)Cl2] (1), [Pd(MeNˆNˆN)ClMe] (2), [Pd(tBuNˆNˆN)Cl2] (3) and [Pd(tBuNˆNˆN)ClMe] (4). Reactions of 1, 2 and 4 with the halide abstractor, NaBAr4 (Ar = 3,5-(CF3)2C6H3), led to the formation of stable tridentate cationic species [Pd(MeNˆNˆN)Cl]+(5), [Pd(MeNˆNˆN)Me]+ (6) and [Pd(tBuNˆNˆN)Cl]+ (7) respectively. The analogous carbonyl linker cationic species [Pd{(3,5-Me2pz-CO)2-py}Cl]+ (9) and [Pd{(3,5-tBu2pz-CO)2-py}Cl]+ (10), prepared by halide abstraction of the neutral complexes [Pd{(3,5-Me2pz-CO)2-py}Cl2] and [Pd{(3,5-tBu2pz-CO)2-py}Cl2] by NaBAr4, were however less stable with t1/2 of 14 and 2 days respectively. Attempts to crystallize 1 and 3 from the mother liquor resulted in the isolation of the salts [Pd(MeNˆNˆN)Cl]2[Pd2Cl6] (11) and [Pd(tBuNˆNˆN)Cl]2[Pd2Cl6] (12). Although when complexes 1–4 were reacted with modified methylaluminoxane (MMAO) or NaBAr4, no active catalysts for ethylene oligomerization or polymerization were formed, activation with silver triflate (AgOTf) produced active catalysts that oligomerized and polymerized phenylacetylene to a mixture of cis-transoidal and trans-cisoidal polyphenylacetylene. 相似文献
392.
Thirupathi N Stricklen PM Liu X Oshel R Guzei I Ellern A Verkade JG 《Inorganic chemistry》2007,46(22):9351-9363
Bicyclic P(CH2NMe)3P was synthesized, and its reactions with MnO2, elemental sulfur, p-toluenesulfonyl azide, BH3.THF, and W(CO)5(THF) were shown to furnish a variety of products in which the PC3 and/or the PN3 phosphorus are oxidized/coordinated. In contrast, reactions of the previously known P(CH2NPh)3P with Mo(0) and Ru(II) precursors were shown to afford products in which only the PC3 phosphorus is coordinated. The contrast in reactivity of P(CH2NR)3P (R = Me, Ph) with the aforementioned reagents is discussed in terms of steric and electronic factors. The new compounds are characterized by analytical and spectroscopic (IR, 1H, 31P, and 13C NMR) methods. The results of crystal and molecular structure X-ray analyses of the previously known compounds P(CH2O)3P and P(CH2NPh)3P and 6 of the 14 new compounds obtained in this investigation are presented. Salient features of these structures and the analysis of the Tolman cone angles calculated from their structural parameters are discussed in terms of the effects of constraint in the bicyclic moieties. Evidence is presented for greater M-P sigma bonding effects on coordination of the PC3 phosphorus of P(CH2NR)3P (R = Me, Ph) than are present in PMe3 analogues of group 6B metal carbonyls. From 1JBP data on the BH3 adducts of P(CH2NMe)3P, it is suggested that the free bases MeC(CH2NMe)3P < P(CH2NMe)3P < (Me2N)3P < P(MeNCH2CH2)3N increase in Lewis basicity at the PN3 phosphorus in the order shown. Substantial differences in 31P chemical shifts in the bicyclic compounds discussed herein relative to their acyclic analogues do not seem to be associated with the relatively small bond angle changes that occur around either the PN3 or the PC3 trivalent phosphorus atoms. 相似文献
393.
Reduction of imines by [2,5-Ph2-3,4-Tol(2)(eta(5)-C(4)COH)]Ru(CO)2H (1) produces kinetically stable ruthenium amine complexes. Reduction of an imine possessing an intramolecular amine was studied to distinguish between inner sphere and outer sphere mechanisms. 1,4-Bn(15)NH(c-C(6)H(10))=NBn (12) was reduced by 1 in toluene-d8 to give 85% of [2,5-Ph2-3,4-Tol(2)(eta(4)-C(4)CO)](CO)(2)RuNHBn(c-C(6)H(10))(15)NHBn (16-RuN,15N), resulting from coordination of the newly formed amine to the ruthenium center, and 15% of trapping product [2,5-Ph2-3,4-Tol(2)(eta(4)-C(4)CO)](CO)(2)Ru(15)NHBn(c-C(6)H(10))NHBn (16-Ru(15)N,N), resulting from coordination of the intramolecular trapping amine. These results provide support for an outer sphere transfer of hydrogen to the imine to generate a coordinatively unsaturated intermediate, which can be trapped by the intramolecular amine. An opposing mechanism, requiring coordination of the imine nitrogen to ruthenium prior to hydrogen transfer, cannot readily explain the observation of the trapping product 16-Ru(15)N,N. 相似文献
394.
Chen SJ Zhang XH Yu X Qiu H Yap GP Guzei IA Lin Z Wu YD Xue ZL 《Journal of the American Chemical Society》2007,129(46):14408-14421
Reaction of d0 Ta(NMe2)5 (1) with O2 yields two aminoxy complexes (Me2N)(n)Ta(eta2-ONMe2)(5-n) (n = 4, 2; 3, 3) as well as (Me2N)4Ta2[eta2-N(Me)CH2NMe2]2(mu-O)2 (4) and (Me2N)6Ta3[eta2-N(Me)CH2NMe2]2(eta2-ONMe2)(mu-O)3 (5) containing novel chelating (aminomethyl)amide-N(Me)CH2NMe2 ligands. The crystal structures of 2-5 have been determined by X-ray crystallography. (Me2N)4Ta(eta2-ONMe2) (2) converts to (Me2N)3Ta(eta2-ONMe2)2 (3) in its reaction with O2. In addition, the reaction of Ta(NMe2)5 with 3 gives 2 only at elevated temperatures. Density functional theory (DFT) calculations have been used to investigate the mechanistic pathways in the reactions of Ta(NMe2)5 (1) with triplet O2. Monomeric reaction pathways in the formation of 2-5 are proposed. A key step is the oxygen insertion into a Ta-N bond in 1 through an intersystem conversion from triplet to singlet energy surface to give an active peroxide complex (Me2N)4Ta(eta2-O-O-NMe2) (A4). The DFT studies indicate that the peroxide ligand plays an important role, including oxidizing an amide to an imine ligand through the abstraction of a hydride. Insertion of Me-N=CH2 into a Ta-amide bond yields the unusual -N(Me)CH2NMe2 ligands. 相似文献
395.
Multiple pathways for dinitrogen activation during the reduction of an Fe Bis(iminepyridine) complex
Reduction of the bis(iminopyridine) FeCl(2) complex {2,6-[2,6-(iPr)(2)PhN=C(CH(3))](2)(C(5)H(3)N)}FeCl(2) using NaH has led to the formation of a surprising variety of structures depending on the amount of reductant. Some of the species reported in this work were isolated from the same reaction mixture, and their structures suggest the presence of multiple pathways for dinitrogen activation. The reaction with 3 equiv of NaH afforded {2-[2,6-(iPr)(2)PhN=C(CH(3))]-6-[2,6-(iPr)(20PhN-C=CH(2)](C(5)H(3)N)}Fe(micro,eta(2)-N(2))Na (THF) (1) containing one N(2) unit terminally bound to Fe and side-on attached to the Na atom. In the process, one of the two imine methyl groups has been deprotonated, transforming the neutral ligand into the corresponding monoanionic version. When 4 equiv were employed, two other dinitrogen complexes {2-[2,6-(iPr)(2)PhN=C(CH(3))]-6-[2,6-(iPr)(2)PhN-C=CH(2)](C(5)H(3)N)}Fe(micro-N2)Na(Et(2)O)(3) (2) and {2,6-[2,6-(iPr)(2)PhN=C(CH(3))](2)(C(5)H(3)N)}Fe(micro-N(2))Na[Na(THF)(2)] (3) were obtained from the same reaction mixture. Complex 2 is chemically equivalent to 1, the different degree of solvation of the alkali cation being the factor apparently responsible for the sigma-bonding mode of ligation of the N(2) unit to Na, versus the pi-bonding mode featured in 1. In complex 3, the ligand remains neutral but a larger extent of reduction has been obtained, as indicated by the presence of two Na atoms in the structure. A further increase in the amount of reductant (12 equiv) afforded a mixture of {2-[2,6-(iPr)(2)PhN=C(CH(3))]-6-[2,6-(iPr)(2)PhN-C=CH(2)](C(5)H(3)N)}Fe-N(2) (4) and [{2,6-[2,6-(iPr)(2)PhN=C(CH(3))](2)(C(5)H(3)N)}Fe-N(2)](2)(micro-Na) [Na(THF)(2)](2) (5) which were isolated by fractional crystallization. Complex 4, also containing a terminally bonded N(2) unit and a deprotonated anionic ligand bearing no Na cations, appears to be the precursor of 1. The apparent contradiction that excess NaH is required for its successful isolation (4 is the least reduced complex of this series) is most likely explained by the formation of the partner product 5, which may tentatively be regarded as the result of aggregation between 1 and 3 (with the ligand system in its neutral form). Finally, reduction carried out in the presence of additional free ligand afforded {2,6-[2,6-(iPr)(2)PhN=C(CH(3))](2)(C(5)H(3)N)}Fe(eta(1)-N(2)){2,6-[2,6-(iPr)(2)PhN=C(CH(3))](20(NC(5)H(2))}[Na(THF)(2)] (6) and {2,6-[2,6-(iPr)(2)PhN=C(CH(3))](2)(C(5)H(3)N)}Fe{2,6-[2,6-(iPr)(2)PhN=C(CH(3))](2)(NC(5)H(2))}Na(THF)(2)) (7). In both species, the Fe metal is bonded to the pyridine ring para position of an additional (L)Na unit. Complex 6 chemically differs from 7 (the major component) only for the presence of an end-on coordinated N(2). 相似文献
396.
Freire F Fisk JD Peoples AJ Ivancic M Guzei IA Gellman SH 《Journal of the American Chemical Society》2008,130(25):7839-7841
We report the development of diacid units that promote formation of a two-stranded parallel beta-sheet secondary structure between peptide segments attached via their N-termini. These linker units are formed by attaching glycine to one carboxyl group of cis-1,2-cyclohexanedicarboxylic acid (CHDA). Parallel sheet formation in water is observed when l-residue strands are attached to the CHDA-Gly unit with either of the two absolute configurations. 相似文献
397.
The fourth-order analogue of the second Painlevé equation is considered. The monodromy manifold for a Lax pair associated with the P 2 2 equation is constructed. The direct monodromy problem for the Lax pair is solved. Asymptotic solutions expressed via trigonometric functions in the Boutroux variables along the rays ? = \(\frac{2}{5}\)π(2n + 1) on the complex plane have been found by the isomonodromy deformations technique. 相似文献
398.
Michael Skoblin Alexey Chudinov Ilia Soulimenkov Vladimir Brusov Viacheslav Kozlovskiy 《Journal of the American Society for Mass Spectrometry》2017,28(10):2132-2142
Numerical simulations of a gas flow through a capillary being a part of mass spectrometer atmospheric interface were performed using a detailed laminar flow model. The simulated interface consisted of atmospheric and forevacuum volumes connected via a thin capillary. The pressure in the forevacuum volume where the gas was expanding after passing through the capillary was varied in the wide range from 10 to 900 mbar in order to study the volume flow rate as well as the other flow parameters as functions of the pressure drop between the atmospheric and forevacuum volumes. The capillary wall temperature was varied in the range from 24 to 150 °C. Numerical integration of the complete system of Navier-Stokes equations for a viscous compressible gas taking into account the heat transfer was performed using the standard gas dynamic simulation software package ANSYS CFX. The simulation results were compared with experimental measurements of gas flow parameters both performed using our experimental setup and taken from the literature. The simulated volume flow rates through the capillary differed no more than by 10% from the measured ones over the entire pressure and temperatures ranges. A conclusion was drawn that the detailed digital laminar model is able to quantitatively describe the measured gas flow rates through the capillaries under conditions considered. 相似文献
399.
Hassan A. Kalviri Felix G?rtner Gang Ye Ilia Korobkov R. Tom Baker 《Chemical science》2015,6(1):618-624
While thermolysis of ammonia-borane (AB) affords a mixture of aminoborane- and iminoborane oligomers, the most selective metal-based catalysts afford exclusively cyclic iminoborane trimer (borazine) and its B–N cross-linked oligomers (polyborazylene). This catalysed dehydrogenation sequence proceeds through a branched cyclic aminoborane oligomer assigned previously as trimeric B-(cyclodiborazanyl)amine-borane (BCDB). Herein we utilize multinuclear NMR spectroscopy and X-ray crystallography to show instead that this key intermediate is actually tetrameric B-(cyclotriborazanyl)amine-borane (BCTB) and a method is presented for its selective synthesis from AB. The reactivity of BCTB upon thermal treatment as well as catalytic dehydrogenation is studied and discussed with regard to facilitating the second dehydrogenation step in AB dehydrocoupling. 相似文献
400.
Ilia A. Guzei Jeffrey S. Dougan Paul M. Treichel 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(9):1060-1061
The title compound, C36H30NP2+·HSO4?·CHCl3, consists of discrete ions and well separated chloroform solvate molecules. The central feature of the structure is O—H?O hydrogen bonding between two hydrogensulfate ions related by a crystallographic inversion centre. The chloroform solvate molecule takes part in a well defined C—H?O hydrogen bond. 相似文献