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IntroductionThepreparativeapproachofaneffectivebilTldslliccatalystisalwaysasubjectofboortantsignificanceinheterogeneouscatalysis.InourrecentstUdies,wefoundthatthebAnetallitcarbonylclustercoCo3(CO)12favorablygivesthebAnetalliccoCo3clusterontheSiOZsubdueaft… 相似文献
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A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of masstransfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performancefor hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of thetraditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersedRh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation ofhigher olefins such as 1-dodecene. 相似文献
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N. V. Kolesnichenko M. V. Sharikova T. Kh. Marzabekova N. A. Markova E. V. Slivinskii 《Russian Chemical Bulletin》1996,45(8):1866-1869
Approaches to increasing the selectivity of water-soluble catalytic systems based on RhCl3 and polycation in hydroformylation of hex- 1-ene were studied. The introduction of a long-chain alkyl radical into the polycation or the use of a higher fatty acid anion results in an increase in the selectivity of the catalytic system at pH > 7 with respect to n-aldehyde to 60 %. This effect is presumably associated with the suppression of isomerization processes due to steric hindrances.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1968–1971, August, 1996. 相似文献
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2-Substituted secondary alcohol o-DPPB esters (o-DPPB=ortho-diphenylphosphanylbenzoyl) have been prepared and their o-DPPB-directed diastereoselective hydroformylation examined. It was found that the diastereoselectivity increased as a function of the steric demand of the substituents both at the stereogenic center and in the alkene 2-position. Hydrolytic cleavage of the o-DPPB group afforded-via the lactols 29-the corresponding lactones 30, the relative configurations of the vicinal stereogenic centers of which were ascertainable by 2D-NOESY spectroscopy. In addition, a crystal structure analysis of the hydroformylation product 2 d provided further confirmation of the relative configuration. Replacement of the ester carbonyl group of the o-DPPB by a methylene unit resulted in significantly worse diastereoselectivity in the course of the hydroformylation (34-->35), which indicates a decisive role for the ester carbonyl function. All the experimental observations were combined in a model of the origin of the 1,2-asymmetric induction during the title reaction. The key feature is the consideration of diastereomeric trigonal-bipyramidal rhodium-hydrido-olefin complexes I and II, capable on the basis of the Hammond postulate of acting as good models for the transition states of the selectivity-determining hydrometalation step. Investigation of these complexes by force-field methods indicated good correlation between theoretically predicted and experimentally determined diastereoselectivities. 相似文献
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有机磷配位铐或钴联基配合物是生产难或醇的工业催化剂,一般公认金属氢化物是反应的催化活性物种.通常反应活性物种仅存在干反应状态下,其结构表征非常困难,在许多研究中只能关联催化剂母体与其活性的关系[‘1;而未能揭示出催化的本质,给催化剂设计造成很大困难,因而对催化剂活性物种的直接表征受到普遍关注.B。wn问、Morrista]及本文作者研究组*均采用加压原位红外光谱方法,在烯烃氢甲酸化反应条件下捕捉到HCO(CO)3L存在的信息·但用相同方法在反应条件下,在RhH键特征吸收谱带195O-2200Cm‘内未观测到错氢化物的Rh-… 相似文献
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在B3LYP/6-31G(d,P)(Rh和P采用LANL2DZ Polar)水平下,研究了有机膦羰基铑催化乙烯的氢甲酰化反应机理,优化了反应中间体、过渡态和产物的结构.结果表明,乙烯的氢甲酰化反应有两条主要的反应路径,经历了乙烯络合、乙烯插入、膦加成、羰基插入、H2的氧化加成和丙醛还原消除及催化剂的再生等过程.乙烯插入、羰基插入、H2的氧化加成和丙醛还原消除过程中三元环的形成是协同进行的.反应以顺式活性催化剂为起始物,H2的氧化加成是反应速度控制步骤,丙酰基的消除反应是不可逆的.理论结果与实验一致. 相似文献