全文获取类型
收费全文 | 275篇 |
免费 | 42篇 |
国内免费 | 59篇 |
专业分类
化学 | 341篇 |
晶体学 | 2篇 |
综合类 | 5篇 |
物理学 | 28篇 |
出版年
2024年 | 1篇 |
2023年 | 7篇 |
2022年 | 13篇 |
2021年 | 16篇 |
2020年 | 26篇 |
2019年 | 11篇 |
2018年 | 18篇 |
2017年 | 8篇 |
2016年 | 13篇 |
2015年 | 18篇 |
2014年 | 20篇 |
2013年 | 22篇 |
2012年 | 14篇 |
2011年 | 19篇 |
2010年 | 13篇 |
2009年 | 18篇 |
2008年 | 6篇 |
2007年 | 18篇 |
2006年 | 9篇 |
2005年 | 4篇 |
2004年 | 17篇 |
2003年 | 12篇 |
2002年 | 11篇 |
2001年 | 7篇 |
2000年 | 5篇 |
1999年 | 3篇 |
1998年 | 6篇 |
1997年 | 4篇 |
1996年 | 13篇 |
1995年 | 4篇 |
1994年 | 4篇 |
1993年 | 2篇 |
1992年 | 4篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1981年 | 1篇 |
排序方式: 共有376条查询结果,搜索用时 296 毫秒
101.
102.
In spite of a potential hydrogen storage material, ammonia borane (AB) was recently found to be a good hydrogenation reagent. It can reduce certain ketones to alcohols or borate esters, and imines to amines. The mechanisms of these reactions are not fully understood yet, and have been systematically studied using high-level CCSD(T) calculations in this work. We have validated theoretically that the forming of alcohols and amines undergoes concerted double-hydrogen transfer (DHT) mechanism. Furthermore, we predicted that the DHT process is facile for more general ketones and imines. For the borate ester formation, we found a pretty high barrier for the experimentally derived stepwise mechanism. Alternatively, we propose that the reaction starts with the DHT process to form alcohol and NH2BH2, followed by alcoholysis of NH2BH2 to form the first B–O bond. This mechanism is in good agreement with the current experimental facts, and also explains why ketone reduction affords different products at different conditions. For these reaction systems, the performances of M06-2x and MP2 (underestimate the barrier by 5–7 kcal/mol, but with right trends) are better than B3LYP and BLYP methods (underestimate the barrier by 0–5 kcal/mol). 相似文献
103.
Synthesis of Ammonia Borane Nanoparticles and the Diammoniate of Diborane by Direct Combination of Diborane and Ammonia 下载免费PDF全文
Yuanzhou Song Nana Ma Prof. Xiaohua Ma Prof. Fang Fang Prof. Xuenian Chen Prof. Yanhui Guo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(18):6228-6233
Pure nanoparticle ammonia borane (NH3BH3, AB) was first prepared through a solvent‐free, ambient‐temperature gas‐phase combination of B2H6 with NH3. The prepared AB nanoparticle exhibits improved dehydrogenation behavior giving 13.6 wt. % H2 at the temperature range of 80–175 °C without severe foaming. Ammonia diborane (NH3BH2(μ‐H)BH3, AaDB) is proposed as the intermediate in the reaction of B2H6 with NH3 based on theoretical studies. This method can also be used to prepare pure diammoniate of diborane ([H2B(NH3)2][BH4], DADB) by adjusting the ratio and concentration of B2H6 to NH3. 相似文献
104.
105.
Contributions to the Chemistry of Phosphorus. 240. On the Reactive Behaviour of Diphosphane-borane, P2H4 · BH3 Under mild temperature conditions, the thermal decomposition of diphosphane-borane ( 1 ) gives rise to the formation of phosphane-borane, PH3 · BH3, and triphosphane-2-borane, PH2? PH(BH3)? PH2 ( 2 ). In the presence of diphosphane-1,2-bis(borane), triphosphane-1,3-bis(borane), BH3? PH2? PH? PH2? BH3 ( 3 ), is formed additionally. The thermolysis product at room temperature is a polymeric solid of varying composition which contains phosphorus, boron, and hydrogen. Compound 1 reacts with metalating agents such as n-BuLi, LiBH4, and NaBH4 to furnish the borane-trihydrogendiphosphide ion, [PH2? PH? BH3]?, which immediately disproportionates to give the corresponding mono-and triphosphane derivatives. In the presence of an excess of THF-borane and in the case of a 1 : 1 molar ratio of 1 : NaBH4, the disproportionation does not occur and the new diphosphide derivative sodium-1,1,2-tris(borane)-1,2,2-trihydrogendiphosphide, Na[(BH3)2PH? PH2BH3] ( 4 ) can be obtained. The action of additional NaBH4 yields the diphosphide dianion with four coordinated BH3 groups. 相似文献
106.
Rama D. Nimmagadda 《Tetrahedron letters》2006,47(21):3505-3508
A convenient one-pot reaction has been developed for the reduction of polycarboxylic acids on aliphatic and aromatic systems to their corresponding alkanes. The reduction utilises either diethylsilane or n-butylsilane as the reducing agent in the presence of the Lewis acid catalyst tris(pentafluorophenyl)borane. 相似文献
107.
本文报道了用9-BBN与1,7-辛二烯-3-醇进行硼氢化反应的结果。这个反应的区域选择性极低,除生成1-辛烯-3-醇(47%)外,同时还生成了7-辛烯-3-醇(41%)和辛醇-3(12%)。 相似文献
108.
Polyhedral borane anions and carboranes that can be constructed formally from the interaction of rings and caps will be stable
with six interstitial electrons. Interstitial electron count is obtained by summing the number of π electrons of the ring
and the electrons of the caps involved in ring cap binding. Thus B7H7
−2 (D5h) has 6 interstitial electrons (none from the B5H5 ring, two each from the twobh caps and two negative charge),mndo calculations on isoelectronic pyramidal molecules B6H6
−4 (C5v), B5H5CH−3 (C5v), B5H5
−4 (C4v), B4H4CH−3 (C4v), B4H4
−4 (T
d) and B3H3CH−3 (C3v) suggests a criterion based on the out-of-plane bendings of the ring B-H bonds to select the best combination of borocycles
and BH or CH caps. Three-membered borocycle prefers CH cap, five-membered borocycle prefers BH cap. The preference of four-membered
ring for BH or CH cap is not as pronounced. The extra stability of B12H12
−2 arises from the geometry of the icosahedron. The relative stabilities ofnido andcloso carboranes follow from these rules. 相似文献
109.
Toshinobu Korenaga 《Journal of fluorine chemistry》2007,128(10):1153-1157
Novel oxazaborolidines B-C6F5 were synthesized by modified protocol from C6F5B(OMe)2 (in place of usual C6F5B(OH)2) and the corresponding amino alcohols, aiming to know the π-π stacking and electron-withdrawing effects of C6F5 group in asymmetric reduction of ketones. Although the results were not simply explained by the expected effects, significant difference was observed in the enantioselectivity between the catalysts with B-C6H5 and B-C6F5. 相似文献
110.
A solution of bis(pentafluorophenyl)borane-dimethyl sulfide complex in hexane was generated by redistribution between tris(pentafluorophenyl)borane and borane-dimethyl sulfide complex. In the resulting solution a stoichiometric hydroboration of alk-1-yne with pinacolborane proceeded well at room temperature to afford (E)-alk-1-enylboronic acid pinacol ester in high yield. Bis(pentafluorophenyl)borane-dimethyl sulfide complex served as a mediator for the hydroboration. 相似文献