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1.
Organolanthanide complexes of the type Cp'(2)LnCH(SiMe(3))(2) (Cp' = eta(5)-Me(5)C(5); Ln = La, Nd, Sm, Lu) and Me(2)SiCp' '(2)LnCH(SiMe(3))(2) (Cp' ' = eta(5)-Me(4)C(5); Ln = Nd, Sm, Lu) serve as efficient precatalysts for the regioselective intermolecular hydroamination of alkynes R'Ctbd1;CMe (R' = SiMe(3), C(6)H(5), Me), alkenes RCH=CH(2) (R = SiMe(3), CH(3)CH(2)CH(2)), butadiene, vinylarenes ArCH=CH(2) (Ar = phenyl, 4-methylbenzene, naphthyl, 4-fluorobenzene, 4-(trifluoromethyl)benzene, 4-methoxybenzene, 4-(dimethylamino)benzene, 4-(methylthio)benzene), di- and trivinylarenes, and methylenecyclopropanes with primary amines R' 'NH(2) (R' ' = n-propyl, n-butyl, isobutyl, phenyl, 4-methylphenyl, 4-(dimethylamino)phenyl) to yield the corresponding amines and imines. For R = SiMe(3), R = CH(2)=CH lanthanide-mediated intermolecular hydroamination regioselectively generates the anti-Markovnikov addition products (Me(3)SiCH(2)CH(2)NHR' ', (E)-CH(3)CH=CHCH(2)NHR' '). However, for R = CH(3)CH(2)CH(2), the Markovnikov addition product is observed (CH(3)CH(2)CH(2)CHNHR' 'CH(3)). For internal alkynes, it appears that these regioselective transformations occur under significant stereoelectronic control, and for R' = SiMe(3), rearrangement of the product enamines occurs via tautomerization to imines, followed by a 1,3-trimethylsilyl group shift to stable N-SiMe(3)-bonded CH(2)=CMeN(SiMe(3))R' ' structures. For vinylarenes, intermolecular hydroamination with n-propylamine affords the anti-Markovnikov addition product beta-phenylethylamine. In addition, hydroamination of divinylarenes provides a concise synthesis of tetrahydroisoquinoline structures via coupled intermolecular hydroamination/subsequent intramolecular cyclohydroamination sequences. Intermolecular hydroamination of methylenecyclopropane proceeds via highly regioselective exo-methylene C=C insertion into Ln-N bonds, followed by regioselective cyclopropane ring opening to afford the corresponding imine. For the Me(2)SiCp' '(2)Nd-catalyzed reaction of Me(3)SiCtbd1;CMe and H(2)NCH(2)CH(2)CH(2)CH(3), DeltaH() = 17.2 (1.1) kcal mol(-)(1) and DeltaS() = -25.9 (9.7) eu, while the reaction kinetics are zero-order in [amine] and first-order in both [catalyst] and [alkyne]. For the same substrate pair, catalytic turnover frequencies under identical conditions decrease in the order Me(2)SiCp' '(2)NdCH(SiMe(3))(2) > Me(2)SiCp' '(2)SmCH(SiMe(3))(2) > Me(2)SiCp' '(2)LuCH(SiMe(3))(2) > Cp'(2)SmCH(SiMe(3))(2), in accord with documented steric requirements for the insertion of olefinic functionalities into lanthanide-alkyl and -heteroatom sigma-bonds. Kinetic and mechanistic evidence argues that the turnover-limiting step is intermolecular C=C/Ctbd1;C bond insertion into the Ln-N bond followed by rapid protonolysis of the resulting Ln-C bond. 相似文献
2.
Xie Ju Yang Yanwu Xi Ziqing Yang Zhenshan Zhang Xuecheng Ni Lubin 《Journal of inclusion phenomena and macrocyclic chemistry》2022,102(9-10):751-761
Journal of Inclusion Phenomena and Macrocyclic Chemistry - The combination of the electron donor and acceptor into a donor–acceptor system can transform the intermolecular charge transfer... 相似文献
3.
本文用定量处理2D NOE实验数据最精确的方法-全弛豫矩阵分析法定量分析了天然有机化合物显脉香茶菜素的相敏NOESY谱,计算出显脉香茶菜素分子中各质子间的交叉弛豫速率,根据1/rtf6∝σtf计算出相应的质子间距离,结果表明:用全弛豫矩阵分析法计算出的质子间距与分子力学计算以及用单晶X-射线衍射法测得的质子间距离基本一致,为用核磁共振方法确定分子在溶液中的三维空间结构提供了可靠的结构参数。 相似文献
4.
WANG Binghe DONG Yanwu TU Haiying WU Shengju SHANG Zhiyuan TONG Jie JIN Xiuchan WANG Ruie 《声学学报:英文版》1995,(3)
I.IntroductionForlongtime,itisoneofveryimportantquestionsinbiomcchanicscirc1estosetupady-namicsmode10fhumancardioscularsystemI'-'1.Peop1ehaveexpectedtostudythecomp1cxcardioscu1arsystemfromtheviewofthesy5temtheoryandtheinformati0ntheory.Wea1sopayattentiontothetheory0fTraditi0nalChinescMedicine(TCM)anditsc1inicalexperience.Thepulseisdrivenbytheheartandtransmittedbyb10odflowthrougharteries.ItgOesa1ongwayfarfromtheheart,andarrivesattheradia1artery.Thusitisaffectedbynoton1ythecon-ditionofthehe… 相似文献
5.
研究了SF-环与P-内射环的关系,构造了SF-环成为P-内射环的一系列条件.证明了SF-环R只要满足其中之一:R的每个极大左理想是有限生成的;特殊右零化子的降链条件;对R的每个极大左理想M,l(M)在R中是本质的,那么R就是P-内射环.在此基础上,利用一定条件下SF-环的P-内射性,发展了SF-环的若干新结果,这些结果部分地拓展了有关文献中的结果. 相似文献
6.
Aiqin Xiang Shuai Xie Fei Pan Hongchang Jin Yiheng Zhai Yanwu Zhu Xianghua Kong Hengxing Ji 《中国化学快报》2021,32(2):830-833
Electrical double-laye r capacitors are widely concerned fo r their high power density,long cycling life and high cycling efficiency.However,their wide application is limited by their low energy density.In this study,we propose a simple yet environmental friendly method to synthesize cobalt and nitrogen atoms co-doped porous carbon(CoAT-NC) material.Cobalt atoms connected with primarily pyridinic nitrogen atoms can be uniformly dispersed in the amorphous carbon matrix,which is benefit for improving electrical conductivity and density of states of the carbon material.Therefore,an enhanced perfo rmance is expected when CoAT-NC is served as electrode in a supercapacitor device.CoAT-NC displays a good gravimetric capacitance of 160 F/g at 0.5 A/g combing with outstanding capacitance retention of 90% at an extremely high current density of 100 A/g in acid electrolyte.Furthermore,a good energy density of30 Wh/kg can be obtained in the organic electrolyte. 相似文献
7.
本文用DSC方法研究了羟酸型含氟离聚体中不同金属离子种类、可离子化基团含量、配位结构单元构型及离子微区大小对离聚体中离子微区稳定性的影响。实验表明:离聚体中金属离子配位能力愈强,羟酸含量愈高,离子微区尺寸愈大,则相应离聚体中离子微区稳定性愈大。铅高聚体>锌离聚体>钙离聚体>钠离聚体。 相似文献
8.
同核RELAY相干传递技术在复杂天然有机化合物1H谱解析中的应用 总被引:1,自引:0,他引:1
用同核化学位移相关谱和同核RELAY谱等二维NMR方法完全归属了复杂天然有机化合物人参皂甙Rb1的1H NMR谱线,并用积算符方法证实一级和二级RELAY实验中观察到的意外交叉峰是通过远程偶合传递的RELAY信号。 相似文献
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