全文获取类型
收费全文 | 183篇 |
免费 | 27篇 |
国内免费 | 3篇 |
专业分类
化学 | 183篇 |
晶体学 | 1篇 |
数学 | 8篇 |
物理学 | 21篇 |
出版年
2022年 | 2篇 |
2021年 | 3篇 |
2020年 | 7篇 |
2019年 | 7篇 |
2018年 | 7篇 |
2017年 | 1篇 |
2016年 | 15篇 |
2015年 | 14篇 |
2014年 | 8篇 |
2013年 | 11篇 |
2012年 | 15篇 |
2011年 | 18篇 |
2010年 | 3篇 |
2009年 | 3篇 |
2008年 | 12篇 |
2007年 | 18篇 |
2006年 | 14篇 |
2005年 | 7篇 |
2004年 | 9篇 |
2003年 | 6篇 |
2002年 | 10篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1983年 | 1篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有213条查询结果,搜索用时 17 毫秒
81.
82.
83.
Hiromi Matsuhashi Daishi Sato Kazushi Arata 《Reaction Kinetics and Catalysis Letters》2004,81(1):183-188
The acidity of sulfated alumina catalysts was studied by analyzing DTG and heat of Ar adsorption together with the isomerization of pentane. The initial acid sites were Brönsted-type, and converted into Lewis-type upon increasing the pretreatment temperature. The heat of Ar adsorption of the most active sulfated alumina was 18.9 kJ mol–1, this value being a little smaller than that of sulfated zirconia (23.6 kJ mol–1).This revised version was published online in December 2005 with corrections to the Cover Date. 相似文献
84.
Kazushi Sorakubo Takeshi Yanai Kenichi Nakayama Muneaki Kamiya Haruyuki Nakano Kimihiko Hirao 《Theoretical chemistry accounts》2003,110(5):328-337
A density functional theory method using partially fixed molecular orbitals (PFMOs) is presented. The PFMOs, which have some fixed molecular orbital coefficients and are non-orthogonal, are a generalization of the extreme localized orbitals (ELMOs) of Couty, Bayse, and Hall (1997) Theor Chem Acc 97:96. A non-orthogonal Kohn-Sham method with these PFMOs is derived, and is applied to molecular calculations on the ionization potential of pyridine, the energy difference between cis- and trans-butadiene, the reaction barrier height of the cyclobutene-cis-butadiene interconversion, and the potential energy curve of the hydrogen shift reaction of hydroxycarbene to formaldehyde. The PFMO Kohn-Sham method reproduces well the results of the full Kohn-Sham method without having a restriction on the molecular orbital coefficients. The difference is less than 0.1 eV in the ionization potential and about 0.1 kcal/mol in the barrier height and in the potential energy calculations. 相似文献
85.
[reaction: see text] Palladium-catalyzed coupling reaction of N,N-dimethylformamide with aryl or alkenyl halides successfully proceeded in the presence of phosphoryl chloride to afford the corresponding tertiary amides in good yields. 相似文献
86.
[reaction: see text] We synthesized a chiral multidentate ligand, (R,R,R,R)-N,N,N',N'-tetra(2-hydroxy-2-phenylethyl)-1,3-xylylene diamine [(R)-2], which can support two metals at adjacent positions. Asymmetric transfer hydrogenation of acetophenone and its derivatives was conducted by using salt-free bimetallic lanthanoid complexes of (R)-2, and the combination of two samarium atoms and (R)-2 was found to be the best catalyst system for asymmetric transfer hydrogenation of aryl ketones in high enantioselectivity (up to >99% ee). 相似文献
87.
A series of aqua-Cr(III)-dioxolene complexes, [Cr(OH(2))(3,5-Bu(2)SQ)(trpy)](ClO(4))(2) (1s), [Cr(OH(2))(3,5-Bu(2)Cat)(trpy)]ClO(4) (1c), [Cr(OH(2))(3,6-Bu(2)SQ)(trpy)](ClO(4))(2) (2), [Cr(OH(2))(Cat)(trpy)]ClO(4) (3), [Cr(OH(2))(Cl(4)Cat)(trpy)]ClO(4) (4), [Cr(OH(2))(3,5-Bu(2)SQ)(Me(3)-tacn)](ClO(4))(2) (5), [Cr(OH(2))(Cat)(Me(3)-tacn)]ClO(4) (6), and [Cr(OH(2))(Cl(4)Cat)(Me(3)-tacn)]ClO(4) (7) (Bu(2)SQ = di-tert-butyl-o-benzosemiquinonate anion, Bu(2)Cat = di-tert-butylcatecholate dianion, Cat = catecholate dianion, Cl(4)Cat = tetrachlorocatecholate dianion, trpy = 2,2':6',2' '-terpyridine, and Me(3)-tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane), were prepared. On the basis of the crystal structures, redox behavior, and elemental analyses of these complexes, dioxolene in 1c, 3, 4, 6, and 7 coordinated to Cr(III) as the catechol form, and the ligand in 1s, 2, and 5 was linked to Cr(III) with the semiquinone form. All the aqua-Cr(III) complexes reversibly changed to the hydroxo-Cr(III) ones upon dissociation of the aqua proton, and the pK(a) value of the aqua-Cr(III) complexes increased in the order 6 > 3 approximately 1c > 7 > 5 approximately 4 > 1s. Hydroxo-Cr(III)-catechol complexes derived from 1c, 3, 4, 6, and 7 did not show any signs of dissociation of their hydroxy proton. On the other hand, hydroxo-Cr(III)-semiquinone complexes were reduced to hydroxo-Cr(III)-catechol in H(2)O/THF at pH 11 under illumination of visible light. 相似文献
88.
The relative acid strength and acid amount of solid acids has been determined from the adsorption and desorption of small molecules, such as argon. The order of activation energy for desorption of Ar from a solid acid, determined using temperature-programmed desorption (TPD), is sulfated zirconia > Cs2.5H0.5PW12O40 > proton-type zeolites > silica–alumina. The adsorption isotherms were analyzed using Langmuir and Henry equations. The Henry-type adsorption isotherms were also analyzed using the theory of Cremer and Flügge. The heat of Ar adsorption was 22 kJ mol−1 for sulfated zirconia and ca. 17 kJ mol−1 for mordenite, ZSM-5, and beta-zeolite. Molybdenum oxides reduced at 623 and 773 K exhibited a large heat of adsorption (19.3 and 19.7 kJ mol−1, respectively), and these materials are classified as superacids. W-Nb mixed-oxides and tungstated tin oxide (calcined at 1373 K), which are newly developed solid acids, had a heat of adsorption of 18.1 and 16.9 kJ mol−1, respectively. The type of acid site could be distinguished by comparing the heat of adsorption of Ar and N2. Our data indicate that Ar is useful for the characterization of solid acids. 相似文献
89.
Treatment of Pd(2)Cl(2)(CNC(6)H(3)Me(2)-2,6)(4) (1) with Mo(2)(O(2)CCF(3))(4) (2) in dichloromethane afforded an infinite zigzag chain [[Pd(2)Cl(2)(CNC(6)H(3)Me(2)-2,6)(4)][Mo(2)(O(2)CCF(3))(4)]](n) (3), where two metal-metal bonded dinuclear Pd-Pd and Mo-Mo units were bridged by chloro atoms. The Mo-Mo distance (2.1312(3) A) of 3 is significantly elongated compared to that of 2 (2.090(4) A) and lies in the range of that of the quadruple Mo-Mo bonded complexes. Such elongation might be attributed to the axial donation of the chloro atoms of the Pd-Pd unit to the Mo-Mo moiety. 相似文献
90.
Shin RY Bennett MA Goh LY Chen W Hockless DC Leong WK Mashima K Willis AC 《Inorganic chemistry》2003,42(1):96-106
The reaction of [(eta(6)-arene)RuCl(2)](2) (arene = C(6)Me(6), 1,4-MeC(6)H(4)CHMe(2)) with a large excess of the dianion of bis(2-mercaptoethyl) sulfide, (HSCH(2)CH(2))(2)S, obtained from deprotonation of the dithiol with freshly prepared NaOMe, gives the deep red, monomeric complexes [(eta(6)-arene)Ru(eta(3)-C(4)H(8)S(3))] (arene = C(6)Me(6) (5), 1,4-MeC(6)H(4)CHMe(2) (6)) in which the dianion is bound to the metal atom through one thioether and two thiolate sulfur atoms. Complex 5 reacts with [(eta(6)-C(6)Me(6))RuCl(2)](2) (4) in a 2:1 mole ratio to give a quantitative yield of the chloride salt of a binuclear cation [((eta(6)-C(6)Me(6))Ru)(2)Cl(mu(2)-eta(2):eta(3)-C(4)H(8)S(3))](+) (7) in which the thiolate sulfur atoms of the [(eta(6)-C(6)Me(6))Ru(eta(3)-C(4)H(8)S(3))] group bridge to a (eta(6)-C(6)Me(6))RuCl unit. This compound is also obtained directly from the reaction of 4 with the dithiolate, if the Ru dimer is used in large excess. The binuclear complex [((eta(6)-C(6)Me(6))Ru)(2)(MeCN)(mu(2)-eta(2):eta(3)-C(4)H(8)S(3))](PF(6))(2).MeCN, (9)(PF(6))(2).MeCN, is obtained by treatment of (7)Cl with NH(4)PF(6) in acetonitrile. Protonation of 5 with HCl gave the mono- and diprotonated derivatives viz. [(eta(6)-C(6)Me(6))Ru(eta(3)-C(4)H(9)S(3))]Cl, (8)Cl, and [(eta(6)-C(6)Me(6))Ru(eta(3)-C(4)H(10)S(3))]Cl(2), (10)Cl(2), respectively. The reaction of 5 with methyl iodide gives both the mono- and di-S-methylated derivatives. Treatment of 5 with dibromoalkanes, Br(CH(2))(n)Br (n = 1-5), effects ring closure to give the (eta(6)-C(6)Me(6))Ru dications containing the trithia mesocyclic zS3 (z = 8-12) ligands, isolated as their PF(6) salts. The X-ray crystal structures of 5, 6, the solvates of (7)Cl and (9)(PF(6))(2), and the trithia mesocyclic Ru complexes (eta(6)-C(6)Me(6))Ru(zS3)(PF(6))(2) (z = 8-11) are reported. 相似文献