全文获取类型
收费全文 | 3211篇 |
免费 | 582篇 |
国内免费 | 520篇 |
专业分类
化学 | 4150篇 |
晶体学 | 41篇 |
力学 | 3篇 |
综合类 | 6篇 |
物理学 | 113篇 |
出版年
2024年 | 5篇 |
2023年 | 36篇 |
2022年 | 48篇 |
2021年 | 86篇 |
2020年 | 130篇 |
2019年 | 111篇 |
2018年 | 95篇 |
2017年 | 90篇 |
2016年 | 169篇 |
2015年 | 193篇 |
2014年 | 222篇 |
2013年 | 305篇 |
2012年 | 252篇 |
2011年 | 217篇 |
2010年 | 201篇 |
2009年 | 199篇 |
2008年 | 224篇 |
2007年 | 231篇 |
2006年 | 220篇 |
2005年 | 181篇 |
2004年 | 184篇 |
2003年 | 168篇 |
2002年 | 83篇 |
2001年 | 86篇 |
2000年 | 75篇 |
1999年 | 66篇 |
1998年 | 56篇 |
1997年 | 62篇 |
1996年 | 59篇 |
1995年 | 55篇 |
1994年 | 32篇 |
1993年 | 36篇 |
1992年 | 34篇 |
1991年 | 24篇 |
1990年 | 18篇 |
1989年 | 12篇 |
1988年 | 11篇 |
1987年 | 4篇 |
1986年 | 9篇 |
1985年 | 5篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1973年 | 2篇 |
排序方式: 共有4313条查询结果,搜索用时 250 毫秒
51.
Brunner H Cattey H Meier W Mugnier Y Stückl AC Wachter J Wanninger R Zabel M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3796-3802
The reaction of the cluster salts [Cp(2*) Nb(CO)(2)](n)[Co(11)Te(7)(CO)(10)] (Cp*=C(5)Me(5); n=1, 2) with excess PMe(2)Ph gave the neutral, dark brown clusters [Co(11)Te(7)(CO)(6)(PMe(2)Ph)(4)] (5) and [Co(11)Te(7)(CO)(5)(PMe(2)Ph)(5)] (6) with 147 metal valence electrons. The new compounds were characterized by IR spectroscopy, elemental analyses, and mass spectrometry. The molecular structure of 6 was determined by X-ray crystallography. Like its precursor anion, it consists of a pentagonal-prismatic [Co(11)Te(7)] core, but with a ligand sphere composed of five CO and five PMe(2)Ph ligands. Detailed electrochemical studies of both reactions reveal that a stepwise substitution of CO ligands in the initial cluster anions takes place leading to intermediate [Co(11)Te(7)(CO)(10-m)(PMe(2)Ph)(m)](n-) ions (m=1-5; n=1, 2). Each of these intermediates is distinguished by at least one oxidation and two reduction waves, giving rise to a total of 21 redox couples and 27 electroactive species. The electron sponge character of the new compounds is particularly pronounced in 5, which exhibits charges n between +1 and -4 corresponding to metal valence electron counts of between 146 and 151. 相似文献
52.
报道了用H_2Fe(CO)_4制备trans-Fe(CO)_3(PR_3)_2的新的羰基取代反应。在 过量质子存在下,H_2Fe(CO)_4中的羰基被活化,中心铁原子对膦的亲核进攻更为 敏感。在这种条件下H_2Fe(CO)_4与膦反应时,首先失去氢生成Fe(CO)_4(PR_3), Fe(CO)_4-(PR_3)再与第二个膦反应可高产率的得到trans-Fe(CO)_3(PR_3)_2。用 PPh_3与Fe(CO)_4(PPh_3)在过量质子存在下反应生成trans-Fe(CO)_3(PR_3)_2,证 实了上述过程。 相似文献
53.
超声波作用下羰基化合物的还原偶联反应 总被引:5,自引:0,他引:5
超声波在一些有机反应中有明显的促进作用「“,Luche等认为超声波的作用有两种主要类型[’j.一类是涉及电子转移的自由基或离子一自由基型反应,由于超声波的空化作用所产生的局部高温高压可以促进电子转移,从而明显地加快反应速度;对大多数离子型反应,超声波只能起到机械的物理作用.我们曾报道偕二卤化合物在Li、Na、Mg等金属作用下产生卡宾的反应是单电子转移过程,该反应可由于超声辐射而大大加速[‘];而在芳基叔脚的断裂反应中,超声波可以促进三苯基俄与金属馊反应生成二苯基脚负离子,但对它进一步的亲核取代反应却没有明… 相似文献
54.
本文利用高压法制备HFe2Co(CO)9(μ3-S),作为原料,经脱质子化作用,再分别与(PPh3)2Cu(NO3)和PPh3AuCl反应,将Ph3Cu-或Ph3Au-联接到原始簇合物的中心骨架上,使簇核扩大,得到了组成为(PPh3)2CuFe2Co(CO)8(μ3-S)和(PPh3)3AuFe2Co(CO)7(μ3-S)的化合物.文中对此两个新化合物进行了IR,UV,1H和31P NMR.元素分析、熔点测定等性质表征,并对(PPh3)2CuFe2Co(CO)7(μ3-S)进行了单晶X-射线衍射分析.两个化合物具有类似的中心骨架,在Fe2和Co原子三角形的上面和下面分别键联着Cu和S,或Au和S原子,构成了三角双锥结构.其中一个簇合物由二个三苯基膦和八个羰基配位,另一个则由三个三苯基膦和七个羰基配位. 相似文献
55.
Hidetake Sakuraba Yoshio Tananaka Fujio Toda 《Journal of inclusion phenomena and macrocyclic chemistry》1991,11(2):195-204
The asymmetric Michael addition of aromatic thiols to 2-cyclohexenone and maleic acid esters has been carried out by utilizing their crystalline cyclodextrin complexes suspended in water. The best chiral induction, 30% enantiomeric excess (ee), was achieved in combinations of 2-cyclohexenone and octyl maleate with the crystalline -cyclodextrin complex of benzenethiol (method A) to afford (S)-3-phenylthiocyclohexanone and (S)-octyl-2-phenylthiosuccinate, respectively, whereas the reaction of benzenethiol with 2-cyclohexenone included in -cyclodextrin (method B) inversely induced the chiral recognition to give the (R)-adduct with 4–9% ee. 相似文献
56.
Yasushi Arakawa Tomoaki MurakamiFumiko Ozawa Yukimi ArakawaShigeyuki Yoshifuji 《Tetrahedron》2003,59(38):7555-7563
Diels-Alder adducts of 1,2-dihydropyridine with maleic and acrylic acid derivatives were stereospecifically converted by way of RuO4 oxidation into new r-2,c-3,c-4,c-5-piperidinetetracarboxylic acid, r-2,t-3,t-4,c-5-piperidinetetracarboxylic acid, r-2,c-3,c-5-piperidinetricarboxylic acid, and r-2,t-3,c-5-piperidinetricarboxylic acid. 相似文献
57.
含磷、硫、氮配原子的钴羰基簇合衍生物的合成和表征 总被引:1,自引:0,他引:1
过渡金属原子簇化学是当今化学学科中非常活跃的研究领域之一 ,这类簇合物大多有着新颖的几何构型和多样化的成键方式 ,并且具有独特的催化性能[1 ] 。迄今为止 ,人们合成了多种含磷、硫、氮等原子的铁、钴、钌等羰基簇合衍生物 ,但其中三种以上原子同时配位的情况并不多见 ,有金振兴等的含C、S、N配原子的三核钴簇[2 ] ;Luga和Cabeza的三钌簇[3 ,4] 以及Chihara等合成的五核钌簇[5] ,其分子中都有P、N、O三原子配位。我们利用复杂的含P、S、N等可配原子的有机配前体与二元钴羰合物反应 ,合成了一系列三核、四核… 相似文献
58.
In the presence of [Ru(terpyridine)(2,6‐pyridinedicarboxylate)], aliphatic and benzylic alcohols are oxidized to the corresponding aldehydes or ketones with high selectivity by using hydrogen peroxide as the oxidant. There is no need for the addition of co‐catalysts or organic solvents. By applying an optimized reaction protocol, high catalyst productivity (turnover number>10 000) and activity (turnover frequency up to 14 800 h?1) has been achieved. 相似文献
59.
Yang L Mayr M Wurst K Buchmeiser MR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(22):5761-5770
The synthesis of novel ruthenium-based metathesis catalysts containing the saturated 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene ligand, that is, [RuCl2(NHC)[=CH-2-(2-PrO)-5-NO(2)-C6H3]] (1) and [Ru(CF3COO)2(NHC)[=CH-2-(2-PrO)-5-NO2-C6H3]] (2) (NHC=1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) is described. Both catalysts are highly active in ring-closing metathesis (RCM) and ring-opening cross-metathesis (ROCM). Compound 1 shows moderate activity in enyne metathesis. Compound 2 is not applicable to enyne metathesis since it shows high activity in the cyclopolymerization of diethyl dipropargylmalonate (DEDPM). Poly(DEDPM) prepared by the action of 2 consists of 95% five-membered rings, that is, poly(cyclopent-1-enevinylene)s, and 5 % of six-membered rings, that is, poly(cyclohex-1-ene-3-methylidene)s. The polymerization proceeds in a nonliving manner and results in polyenes with broad polydispersities (1.9< or =PDI< or =2.3). Supported analogues of 2 were prepared by immobilization on hydroxymethyl-Merrifield resin and a monolithic support derived from ring-opening-metathesis polymerization (ROMP). Catalyst loadings of 1 and 2.5%, respectively, were obtained. Both supported versions of 2 showed excellent reactivity. With 0.24-2% of the supported catalysts, yields in RCM and ROCM were in the range of 76-100%. Leaching of ruthenium was low and resulted in Ru contaminations of the products of less than 0.000014% (0.14 ppm). 相似文献
60.
Zareen Ahkter Andrew J. Edwards Scott L. Ingham Jack Lewis Ana M. Martin Castro Paul R. Raithby Gregory P. Shields 《Journal of Cluster Science》2000,11(1):217-226
The reaction of the di-gold cation [Au2(dppx)]2+ with the heptanuclear cluster dianion [Os7(CO)20]2– affords the mixed metal cluster [Os7(CO)20{Au2(dppx)}] (x=m (1), e (2), b (3)). On standing, in solution, this complex undergoes decarbonylation to give the cluster [Os7(CO)19{Au2(dppx)}] (x=m (4), e (5), b (6)). The complexes have been characterised spectroscopically, and an X-ray structure determination of the dppm derivative shows that it contains a metal core based on an Os7 edge-bridged bicapped tetrahedron with the two
3-Au atoms capping adjacent triangular Os3 faces of the central tetrahedron. In an analogous reaction, the carbido anion [Os7(H)C(CO)19]– affords the neutral cluster [Os7C(CO)19{Au2(dppm)}] (7) when treated with [Au2(dppm)]2+ in the presence of base. 相似文献