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101.
Joseph S. Alper Robert I. Gelb Marietta H. Schwartz 《Journal of inclusion phenomena and macrocyclic chemistry》1991,11(4):333-348
Complexation stoichiometries and formation constants of tri- and tetra-protonated forms of 1,4,8,12-tetraazacyclopentadecane with NO
3
–
, Cl–, IO
3
–
and SO
4
2–
ions are determined by pH potentiometric and13C NMR spectrometric measurements. Estimates of H and S are obtained from the values of the temperature dependent formation constants and acid dissociation constants. All four anions form only 1 : 1 complexes with the triprotonated amine species. NO
3
–
and Cl– form 1 : 1 complexes only with the tetraprotonated amine, while IO
3
–
and SO
4
2–
form both 1 : 1 and 2 : 1 complexes. The complexation behavior is interpreted in terms of solvation and internal hydrogen bonding interactions. 相似文献
102.
The most stable structure of CB2H3
–, as established computationally, is the aromatic diboracyclopropenyl (diboriranyl) anion (5), while open-chainC
2v, isomer H2BCBH (7) is only 3 kcal/mol higher in energy at the QCISD(T)/6-311 +G**//MP2/6-31+G*+ZPE (HF/6-31 +G*). The 47-kcal/mol barrier between cyclic,5, and open-chain,7, structures suggests that both of them may be observed. The aromatic stabilization energy of the diboriranyl anion (18 kcal/mol) is half the value in the isoelectronic cyclopropenium ion, C3H3
+. The computed, by IGLO method (5a), and experimental (6a) chemical shifts,(13C) and(11B), agree within 4 ppm range. The theoretical vibrational frequencies of the most stable isomers,5 and7, are presented for experimental verification of these species. 相似文献
103.
An accurate structure refinement of the deuterated analog of the cesium lithium acid sulfate, formerly identified as ‘Cs1.5Li1.5H(SO4)2’, has been carried out using neutron diffraction methods. Like the protonated material reported earlier (Merinov et al., Solid State Ionics 69 (1994) 53), the compound is cubic, , however, the correct stoichiometry is Cs3Li(DSO4)4. There are four formula units per unit cell and six atoms in the asymmetric unit. The lattice constant measured in this work is a=11.743(2) Å, comparable to the earlier results. The structure contains one disordered hydrogen bond, formed between O(2) atoms and located on two of the edges of the single LiO4 tetrahedron. The Li site occupancy is , as is that of the deuterium site. This level of site occupancies is consistent with a structure in which hydrogen bonds are formed only when the lithium site is unoccupied, and explains the otherwise close proximity of the Li and D atoms, 1.394(10) Å. This unusual structural feature furthermore leads to a fixed stoichiometry, as confirmed here by chemical analysis of both the deuterated and protonated materials, despite the partial occupancy of the lithium and deuterium (hydrogen) atom sites. 相似文献
104.
A ChaiyanurakkulR Jitchati M KaewpetS Rajviroongit Y Thebtaranonth P ThongyooW Watcharin 《Tetrahedron》2003,59(49):9825-9837
Deprotonation of an oxiranyl β-proton takes place in a stereoselective manner providing the corresponding oxiranyl ‘remote’ anion. The anion is stabilized by chelation between the lithium and the carbonyl moiety of an ester, lactone, imide, or keto-group in the form of a five-membered cyclic intermediate. Certain ester-stabilized oxiranyl anions are stable and can be left in THF solution at −78°C for several hours. The generated anions undergo a stereoselective alkylation reaction to provide products, which could be useful intermediates in the synthesis of bioactive naturally occurring α-methylene bis-γ-butyrolactones. 相似文献
105.
Sulfonylation of alkenes through photoredox‐catalyzed functionalization of alkenes with thiourea dioxide under visible‐light irradiation is achieved. The reaction of alkenes, thiourea dioxide and electrophiles provides a green and efficient access to alkyl sulfones and sulfonamides. A broad reaction scope is presented with good functional group compatibility and excellent regioselectivity. A plausible mechanism involving a radical addition process with sulfur dioxide radical anion (SO2‐) derived from the oxidation of sulfur dioxide anion (SO22–) is proposed, which is supported by fluorescence quenching experiments. 相似文献
106.
Anand VG Venkatraman S Rath H Chandrashekar TK Teng W Ruhlandt-Senge K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(10):2282-2290
Modified octaphyrins with 34pi electrons have been synthesized and characterized following a simple synthetic methodology. An acid-catalyzed alpha,alpha coupling of tetrapyrranes containing furan, thiophene and selenophene rings resulted in the formation of the respective octaphyrins in relatively good yield. Solution studies by (1)H NMR and 2D NMR methods and single crystal Xray structural characterization reveal an almost flat structure with two heterocyclic rings inverted. Specifically, in 14 two selenophene rings (one on each biselenophene unit) are inverted while in 15 two furan rings (one on each bifuran unit) are inverted when the meso substituent are mesityl groups. On changing the mesityl substituent to m-xylyl group as in 19, the location of ring inversion shifts to pyrrole rings (one on each bipyrrole unit) indicating the dependence of structure on the meso substituents. UV/Vis studies, both in freebase and protonated forms reveal typical porphyrinic character and the aromatic nature of the octaphyrins. The Deltadelta values evaluated by (1)H NMR spectroscopy also support their aromatic nature. The protonated forms of octaphyrins bind TFA anion in a 1:2 ratio. The TFA anions are located one above and below the plane of the octaphyrin macrocycle and they are held by weak electrostatic NH-O interactions similar to that observed for protonated rubyrins. However, in the present case, there is an additional non-electrostatic CH-O interaction involving beta-CH of the inverted heterocyclic ring and the carbonyl oxygen of the TFA. Furthermore, inter molecular interactions between the Cbond;H of the meso-mesityl group and the fluorine of CF(3) group of bound TFA leads to the formation of one-dimensional supramolecular arrays with interplanar distance of 13 A between two octaphyrins. 相似文献
107.
无机阴离子的毛细管电泳分析 总被引:9,自引:2,他引:9
本文研究了常见无机阴离子的毛细管电泳规律,考察了分离电压、电解质熔液组成、浓度、pH值等对分离的影响,建立了高效、快速的无机阴离子毛细管电泳分析方法。在选定的实验条件下,各种常见无机阴离子在5min内达到完全分离,对Br^-和Cl^-的分离柱效每米可达76万理论板数。迁移时间的相对标准偏差小于1%,峰面积的相对标准偏差小于5%,各离子的最低检测浓度为0.05 ̄0.5μg/ml。 相似文献
108.
To avoid changes in the original As species distribution in natural water after sampling, a method of immediate separation
of As(V) by anion exchange at the sampling site was developed. The procedure consists of two steps. The total concentration
of arsenic is determined in one part of the water sample acidified on site. Another part of the water samples is pressed through
a column filled with an anion exchanger. The As(III) species that is not redox-stable remains in the effluent of the sorbents
column and can be analyzed with conventional methods after stabilization by addition of conc. HNO3. As(V) is sorbed by the exchanger material. The As(V) concentration can be calculated as the difference between Assol and As(III), neglecting very low contents of methylated species.
Oxidation of Fe(II) by air followed by co-precipitation of arsenic with iron hydroxide was applied in field experiments to
minimize the As concentration in seepage and mining water. 相似文献
109.
Charge-discharge Behavior of Surface-coated LiMn2O3.95F0.05 Cathode Materials at High Temperature 总被引:1,自引:0,他引:1
ZhaoYongCHEN YanRongLI ZuoLongYU 《中国化学快报》2003,14(12):1296-1298
With inorganic salts such as LiNO3, Li2CO3, surface-coated LiMn2O3.95F0.05 were prepared by melt-impregnation method. When these surface-coated LiMn2O3.95F0.05 were used as cathode materials, their charge-discharge characters were carefully compared. As a result, they exhibited good charge-discharge properties at 50℃ high temperature. Especially, LiNO3 surface-coated LiMn2O3.9F50.05 retained nearly 80% initial reversible capacity after 130 cycles at 50℃. 相似文献
110.
用混合床离子色谱柱同时测定阴阳离子 总被引:3,自引:0,他引:3
将阴离子交换树脂和阳离子交换换树脂混合后填充在一根色谱柱中,即所谓阴阳离子混合床柱。研究了阴阳离子在此混合柱上的保留行为并探讨了其保留机理。 相似文献