全文获取类型
收费全文 | 6505篇 |
免费 | 787篇 |
国内免费 | 173篇 |
专业分类
化学 | 6773篇 |
晶体学 | 55篇 |
力学 | 283篇 |
综合类 | 7篇 |
数学 | 165篇 |
物理学 | 182篇 |
出版年
2024年 | 6篇 |
2023年 | 87篇 |
2022年 | 114篇 |
2021年 | 158篇 |
2020年 | 266篇 |
2019年 | 194篇 |
2018年 | 112篇 |
2017年 | 113篇 |
2016年 | 258篇 |
2015年 | 281篇 |
2014年 | 293篇 |
2013年 | 393篇 |
2012年 | 386篇 |
2011年 | 397篇 |
2010年 | 361篇 |
2009年 | 392篇 |
2008年 | 480篇 |
2007年 | 506篇 |
2006年 | 394篇 |
2005年 | 405篇 |
2004年 | 428篇 |
2003年 | 350篇 |
2002年 | 116篇 |
2001年 | 111篇 |
2000年 | 95篇 |
1999年 | 131篇 |
1998年 | 119篇 |
1997年 | 108篇 |
1996年 | 93篇 |
1995年 | 103篇 |
1994年 | 45篇 |
1993年 | 32篇 |
1992年 | 28篇 |
1991年 | 20篇 |
1990年 | 8篇 |
1989年 | 11篇 |
1988年 | 12篇 |
1987年 | 11篇 |
1986年 | 3篇 |
1985年 | 6篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1975年 | 4篇 |
1974年 | 2篇 |
1969年 | 2篇 |
1957年 | 2篇 |
排序方式: 共有7465条查询结果,搜索用时 15 毫秒
251.
Dr. Yungen Liu Dr. Chun-Wai Tse Dr. Kar-Yee Lam Dr. Xiao-Yong Chang Dr. Xiangguo Guan Meng-Yao Chao Dr. Jie-Sheng Huang Prof. Dr. Chi-Ming Che 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(46):10828-10833
Ruthenium(II) complexes bearing a tridentate bis(N-heterocyclic carbene) ligand reacted with iminoiodanes (PhI=NR) resulting in the formation of isolable ruthenium(III)–amido intermediates, which underwent cleavage of a C−N bond of the tridentate ligand and formation of an N-substituted imine group. The RuIII–amido intermediates have been characterized by 1H NMR, UV/Vis, ESI-MS, and X-ray crystallography. DFT calculations were performed to provide insight into the reaction mechanism. 相似文献
252.
Markus Balmer Dr. Florian Weigend Prof. Dr. Carsten von Hänisch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(19):4914-4919
The N-heterocyclic carbene (NHC)-stabilized phosphinidenide, SIMesPK [SIMes=1,3-bis(2,4,6-trimethylphenyl)imidazolidine-2-ylidene], was used as an (NHC)P-transfer reagent for the synthesis of the low-valent Group 14 ate complexes K[(SIMesP)3E] (E=Ge: 2 , Sn: 3 , Pb: 4 ), which were characterized by 1H NMR, 31P NMR, IR spectroscopy as well as elemental and X-ray analysis. Furthermore, SIMesPK was used in reactions with potassium amides and alkoxides to form the molecular phosphorus–potassium clusters [K4(SIMesP)2(hmds)2] [ 5 , hmds=N(SiMe3)2] and [K6(SIMesP)2(OtBu)4] ( 6 ). Finally, the reaction of SIMesPK with Li[Al(OC4F9)4] led to the potassium-rich ionic compound [(SIMesP)4K5][Al(OC4F9)4] ( 7 ). 相似文献
253.
254.
《Journal of Coordination Chemistry》2012,65(22):3914-3922
Two octacyanometallate-based NiII–MIV [M?=?Mo(1), W(2)] bimetallic assemblies chelated with tetradentate macrocyclic ligands have been synthesized by slow diffusion and characterized structurally. In both complexes, M and Ni centers acting as linker and connector, respectively, are connected by M–CN–Ni–NC–M linkages to form a 3-D diamond-type topological network. Magnetic behaviors of both complexes show a very weak antiferromagnetic interaction between NiII ions mediated by the diamagnetic [M(CN)8]4? bridges. 相似文献
255.
256.
Efficient and modular syntheses of chiral 2-(2-hydroxyaryl)alcohols (HAROLs), novel 1,4-diols carrying one phenolic and one alcohol hydroxyl group, have been developed which led to generation of a small library of structurally diverse HAROLs in enantiomerically pure form. Of the different HAROLs examined, a HAROL based on the indan backbone exhibited the highest activity and enantioselectivity in the 1,2-addition of certain organometallic compounds to aldehydes in the presence of Ti(OiPr)4 (up to 97% y, 88% ee) and performed as a hydrogen-bond donor organocatalyst in the Morita-Baylis-Hillman reaction, promoted by trialkylphosphines. 相似文献
257.
Dr. Valerie H. L. Wong Dr. Sai V. C. Vummaleti Prof. Luigi Cavallo Dr. Andrew J. P. White Prof. Steven P. Nolan Dr. King Kuok Hii 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(37):13320-13327
A general synthetic route was used to prepare 15 new N‐heterocyclic carbene (NHC)–AgI complexes bearing anionic carboxylate ligands [Ag(NHC)(O2CR)], including a homologous series of complexes of sterically flexible ITent ligands, which permit a systematic spectroscopic and theoretical study of the structural and electronic features of these compounds. The complexes displayed a significant ligand‐accelerated effect in the intramolecular cyclisation of propargylic amides to oxazolidines. The substrate scope is highly complementary to that previously achieved by NHC–Au and pyridyl–AgI complexes. 相似文献
258.
Koushik Saha Benson Joseph Rongala Ramalakshmi Dr. R. S. Anju Dr. Babu Varghese Prof. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(23):7871-7878
Thermolysis of [Cp*Ru(PPh2(CH2)PPh2)BH2(L2)] 1 (Cp*=η5‐C5Me5; L=C7H4NS2), with terminal alkynes led to the formation of η4‐σ,π‐borataallyl complexes [Cp*Ru(μ‐H)B{R‐C=CH2}(L)2] ( 2 a – c ) and η2‐vinylborane complexes [Cp*Ru(R‐C=CH2)BH(L)2] ( 3 a – c ) ( 2 a , 3 a : R=Ph; 2 b , 3 b : R=COOCH3; 2 c , 3 c : R=p‐CH3‐C6H4; L=C7H4NS2) through hydroboration reaction. Ruthenium and the HBCC unit of the vinylborane moiety in 2 a – c are linked by a unique η4‐interaction. Conversions of 1 into 3 a – c proceed through the formation of intermediates 2 a – c . Furthermore, in an attempt to expand the library of these novel complexes, chemistry of σ‐borane complex [Cp*RuCO(μ‐H)BH2L] 4 (L=C7H4NS2) was investigated with both internal and terminal alkynes. Interestingly, under photolytic conditions, 4 reacts with methyl propiolate to generate the η4‐σ,π‐borataallyl complexes [Cp*Ru(μ‐H)BH{R‐C=CH2}(L)] 5 and [Cp*Ru(μ‐H)BH{HC=CH‐R}(L)] 6 (R=COOCH3; L=C7H4NS2) by Markovnikov and anti‐Markovnikov hydroboration. In an extension, photolysis of 4 in the presence of dimethyl acetylenedicarboxylate yielded η4‐σ,π‐borataallyl complex [Cp*Ru(μ‐H)BH{R‐C=CH‐R}(L)] 7 (R=COOCH3; L=C7H4NS2). An agostic interaction was also found to be present in 2 a – c and 5 – 7 , which is rare among the borataallyl complexes. All the new compounds have been characterized in solution by IR, 1H, 11B, 13C NMR spectroscopy, mass spectrometry and the structural types were unequivocally established by crystallographic analysis of 2 b , 3 a – c and 5 – 7 . DFT calculations were performed to evaluate possible bonding and electronic structures of the new compounds. 相似文献
259.
260.