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981.
Fokin AA Kiran B Bremer M Yang X Jiao H von Rague Schleyer P Schreiner PR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(9):1615-1628
A series of charged and neutral four-center n-electron (4c-ne, n = 1-4) molecules based on the adamantane framework, but which include combinations of boron, nitrogen, and phosphorus atoms at bridgehead positions, were studied computationally at the B3LYP/6-31G* level of density functional theory (DFT). The three-dimensional aromaticity, observed earlier for the 1,3,5,7-bisdehydroadamantane dication (1), is found to be general for 4c-2e electron systems. The degree of electron delocalization, evaluated by energetic, geometric, and various magnetic criteria, is quite independent of the molecular symmetry (point groups vary from Td to Cs), the degeneracy of the orbitals, the molecular charges, and the nature of the atoms participating in the delocalized bonding. Although the multiple positive (e.g., in 1 and some of the heteroatom systems) and multiple negative charges are strongly repulsive, the rigid adamantane frameworks help hold the bridgehead atoms within bonding distances with the fewer available electrons. The corresponding 4c-1e doublets are approximately half as aromatic as the 4c-2e singlets based on the same criteria. However, the three-electron systems may either adopt distorted but still four-center delocalized structures, or alternative 3c-2e two-dimensional arrangements in which the fourth bridgehead atom is more distant. There is no need to derive special rules for each point group for 4c-ne systems. Although the three-dimensional stabilization is computed to be quite appreciable, ranging between 10 and 50 kcalmol(-1), this delocalization energy is generally not sufficient to overcome distortion due to strain in higher homologues of 1 and in analogous noncage systems. Among the various 4c-2e homoadamantanedehydro dications studied, only the 1,8-dehydrohomoadamandiyl-3,6-dication forms a three-dimensional aromatic system. 相似文献
982.
碱处理笼形聚偕氨肟树脂(BCAO)对羧酸表现出强的吸附能力。一元羧酸在BCAO树脂上以多层吸附为主要特征。二元和三元羧酸则以单层吸附占优势。后者可能是以双阴离子的一个负极吸着在BCAO树脂表面,形成了对其他羧酸阴离子起排斥作用的负离子场。另外,双阴离子也有可能和两个氨基结合形成次级交联,妨碍着其他离子迁移和扩散。 相似文献
983.
984.
The palladium-catalyzed hydrostannolysis of α-disubstituted allyl β-keto esters yields the corresponding tributyltin β-keto carboxylates which loose carbon dioxide at very moderate temperature, thus leading to the regiospecific formation of tributyltin tetrasubstituted enolates. 相似文献
985.
测定了Na-β氧化铝管在NaOH、NaOH-KOH、NaOH-(CH_3)_4NOH以及NaOH-NaCl四种溶液的浓差电池体系中的电动势, 求得Na-β氧化铝与NaOH水溶液之间的界面电势Δφ。结果表明: 在NaOH、NaOH-NaCl水溶液中, Δφ与loga_2(Na~+)/a_1(Na~+)之间的关系服从Nernst公式; K~+离子的存在影响Δφ值, 而OH~-、(CH_3)_4N~+贴无影响。探讨了用β氧化铝在高浓碱性Na~+水溶液中做Na~+离子选择性电极的可能性。 相似文献
986.
Weidong Li Yuan Liu Boyang Wang Haoqiang Song Zhongyi Liu Siyu Lu Bai Yang 《中国化学快报》1990,30(12):2323-2327
A facile, low-cost, green, kilogram-scale synthesis of high quality CQDs were synthesized. The throughput of CQDs is 1.4975 kg in one pot and the as-prepared CQDs have a highly crystalline hexagonal structure with remarkable solubility, stability, and biocompatibility. It showed outstanding electrocatalytic activity, Fe3+ sensitivity and good biocompatibility. 相似文献
987.
The highly stereoselective intramolecular metal carbenoid insertion reaction of sulfinimine-derived delta-amino alpha-diazoesters is used to prepare cis-5-tert-butylproline. A concerted or nearly concerted metal carbenoid N-H insertion reaction mechanism is proposed. 相似文献
988.
论述了用激光解吸电离谱法分析富勒烯。因在电离过程中富勒分子不发生裂解,因此这种方法可直接用于富勒烯混合物的分析而勿需任何预分离。还给出了用本法分析较大、较稳定富勒烯分子的质谱图。 相似文献
989.
Kaishuo Yang Ehsan Sadeghi Pouya Libin Liu Dr. Ming Li Dr. Xiaoxian Yang Dr. Neil Robinson Prof. Eric F. May Prof. Michael L. Johns 《Chemphyschem》2022,23(4):e202100794
Understanding the behaviour of short-chain hydrocarbons confined to porous solids informs the targeted extraction of natural resources from geological features, and underpins rational developments in separation, storage and catalytic conversion processes. Herein, we report the application of low-field (12.7 MHz) 1H nuclear magnetic resonance (NMR) relaxation measurements to characterise ethane dynamics within mesoporous silica materials exhibiting mean pore diameters between 6 and 50 nm. Our measurements provide NMR-based adsorption isotherms within the range 25–50 bar and at ambient temperature, incorporating the ethane condensation point (40.7 bar at our experimental temperature of 23.6 °C). The quantitative nature of the acquired data is validated via a direct comparison of NMR-derived excess adsorption capacities with ex situ gravimetric ethane adsorption measurements, which are demonstrated to agree to within 0.2 mmol g−1 of the observed ethane capacity. NMR relaxation time distributions are further demonstrated as a means to decouple interparticle and mesopore dominated adsorption phenomena, with unexpectedly rapid relaxation rates associated with interparticle ethane gas confirmed via a direct comparison with NMR self-diffusion analysis. 相似文献
990.
萃取分光光度法测定水和硫酸中的硒 总被引:3,自引:0,他引:3
本文提出一种测定硒的分光光度法。在酸性介质中,四价硒氧化I成为I3,I3-和结晶紫形成的离子缔合物用二甲苯萃取,进行分光光度测定。硒的检出限是0.05μg/mL。用磷酸和EDTA消除Fe^3+,Pb^2+,Hg^2+等离子的干扰影响。本法可不和硫酸中四价硒。 相似文献