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71.
A chiral supramolecular assembly encapsulates the two cationic ruthenium sandwich complexes [CpRu(eta(6)-C(6)H(6))](+) and [CpRu(p-cymene)](+). The host-guest complexes K(11)[CpRu(eta(6)-C(6)H(6)) subset Ga(4)L(6)] (2) and K(11)[CpRu(p-cymene) subset Ga(4)L(6)] (3) were characterized by one- and two-dimensional NMR techniques as well as by electrospray mass spectrometry. Encapsulation of the prochiral complex [CpRu(p-cymene)](+) by the chiral host renders enantiotopic protons diastereotopic as evidenced by (1)H NMR spectroscopy. 相似文献
72.
Rolf Niedermayer 《Angewandte Chemie (International ed. in English)》1975,14(4):212-218
Synthesis of organometallic materials can be accomplished in many cases by cocondensation of metal atoms and organic molecules at low temperatures. The reaction kinetics is determined by the competition between metal cluster growth and formation of the organometallic compound. Interesting compounds may contain one or more metal atoms; the latter type could be obtained by reaction between a cluster containing the desired number of metal atoms and an organic molecule. A precise knowledge of the events occurring on condensation of metal atoms and cluster formation can therefore be of value in the control of chemical synthesis. These phenomena have been investigated in connection with the study of the growth of thin metallic films, both experimentally and theoretically. Direct observation of the formation of very small clusters is difficult. The good agreement between experimental results and recent calculations for the development of large clusters, however, allows reliable theoretical conclusions for the first stages of adsorption and cluster formation. The present contribution describes experimental work on film growth and relevant theoretical concepts, and an attempt is made to develop applications to organometallic synthesis. 相似文献
73.
Sánchez-Moreno MJ Gómez-Coca RB Fernández-Botello A Ochocki J Kotynski A Griesser R Sigel H 《Organic & biomolecular chemistry》2003,1(10):1819-1826
The synthesis of (1H-benzimidazol-2-yl-methyl)phosphonic acid, H2(Bimp)+/-, is described: 2-chloromethylbenzimidazole was reacted with ethylchloroformate to give 1-carboethoxy-2-chloromethylbenzimidazole which was treated with trimethyl phosphite and after hydrolysis with aqueous HBr H2(Bimp)+/- was obtained. In H2(Bimp)+/- one proton is at the N-3 site and the other at the phosphonate group; both acidity constants were determined in aqueous solution by potentiometric pH titrations (25 degrees C; I = 0.1 M, NaNO3) and this furnished the pKa values of 5.37 +/- 0.02 and 7.41 +/- 0.02, respectively. The acidity constant for the release of the primary proton from the P(O)(OH)2 group of H3(Bimp)+ was estimated: pKa = 1.5 +/- 0.2. Moreover, Bimp2- can be further deprotonated at its neutral (N-1/N-3)H site to give the benzimidazolate residue, but this reaction occurs only in strongly alkaline solution (KOH); application of the H_ scale developed by G. Yagil (J. Phys. Chem., 1967, 71, 1034) together with UV spectrophotometric measurements gave pKa = 14.65 +/- 0.12. Comparisons with acidity constants taken from the literature show that this latter pKa value is far too large and this allows the conclusion that an intramolecular hydrogen bond is formed between the (N-1/N-3)H site and the phosphonate group of Bimp2-; the formation degree of this hydrogen-bonded isomer is estimated to be 98 +/- 2%. The general relevance of this and the other results are shortly discussed and the species distribution for the Bimp system in dependence on pH is provided. 相似文献
74.
Several highly activated 2,3′-biindolyls were prepared from methyl 5,6-dimethoxyindole-2-carboxylate and oxindoles. The 2,3′-biindolyls were further transformed into a hydroxy indolo[3,2-a]carbazole and a bisindole amide. 相似文献
75.
Determination of titanium by adsorption voltammetry with 4-(2-pyridylazo) resorcinol 总被引:2,自引:0,他引:2
Summary Titanium (IV) forms a complex with 4-(2-pyridylazo) resorcinol (PAR) in weakly acidic solutions. This complex can be used to determine titanium by adsorption voltammetry at a stationary Hg-electrode. The experimental conditions for the determination are described. The current-concentration curve is linear from 0.15–4.8 ng/g. Ti at a deposition time of 3 min, the detection limit lies at 0.1 ng/g. The influence of foreign ions was investigated. The determination can be carried out in the presence of a 1000-fold excess of iron by the standard addition method, albeit with decreased sensitivity. 相似文献
76.
An investigation has been carried out on the influence of the velocity of voltage change, of the radius of the capillary and of the size of the electrodes on the decrease of the peak current caused by back-diffusion in anodic amalgam voltammetry. 相似文献
77.
Biological soil crusts are important cryptogamic communities covering the sand dunes of the north-western Negev. The biological crusts contain cyanobacteria and other free-living N(2)-fixing bacteria and are hence able to fix atmospheric nitrogen (N). This is why they are considered to be one of the main N input pathways into the desert ecosystem. However, up to now, in situ determinations of the N(2) fixation in the field are not known to have been carried out. We examined the natural (15)N method to determine the biological N(2) fixation by these soil crusts under field conditions. This novel natural (15)N method uses the lichen Squamarina with symbiotic green algae--which are unable to fix N(2)--as a reference in order to determine N(2) fixation. Depending on the sampling location and year, the relative biological fixation of atmospheric nitrogen was estimated at 84-91% of the total N content of the biological soil crust. The cyanobacteria-containing soil lichen Collema had a fixation rate of about 88%. These fixation rates were used to derive an absolute atmospheric N input of 10-41 kg N ha(-1) year(-1). These values are reasonable results for the fixation of atmospheric N(2) by the biological crusts and cyanolichens and are in agreement with other comparable lab investigations. As far as we are aware, the results presented are the first to have been obtained from in situ field measurements, albeit only one location of the Negev with a small number of samples was investigated. 相似文献
78.
Wouter Post Arijana Susa Rolf Blaauw Karin Molenveld Rutger J. I. Knoop 《高分子科学杂志,C辑:聚合物评论》2020,60(2):359-388
AbstractThe outstanding performance of conventional thermosets arising from their covalently cross-linked networks directly results in a limited recyclability. The available commercial or close-to-commercial techniques facing this challenge can be divided into mechanical, thermal, and chemical processing. However, these methods typically require a high energy input and do not take the recycling of the thermoset matrix itself into account. Rather, they focus on retrieving the more valuable fibers, fillers, or substrates. To increase the circularity of thermoset products, many academic studies report potential solutions which require a reduced energy input by using degradable linkages or dynamic covalent bonds. However, the majority of these studies have limited potential for industrial implementation. This review aims to bridge the gap between the industrial and academic developments by focusing on those which are most relevant from a technological, sustainable and economic point of view. An overview is given of currently used approaches for the recycling of thermoset materials, the development of novel inherently recyclable thermosets and examples of possible applications that could reach the market in the near future. 相似文献
79.
Veronika Gemmer-Colos und Rolf Neeb 《Fresenius' Journal of Analytical Chemistry》1978,293(4):290-294
Zusammenfassung Kleine Mengen Ni, Cu und Zn in wäßrigen Lösungen können nach Ausschütteln ihrer Dipropyldithiocarbamatochelate gas-chromatographisch bestimmt werden. Arbeitsbedingungen für den 0,01–1 ppm-Bereich werden angegeben. Die Reproduzierbarkeit der Bestimmung wird durch Zusatz eines inneren Standards verbessert.
Dialkyldithiocarbamates as reagents for the gas-chromatographic determination of metalsII. Determination of zinc, copper and nickel as dipropyldithiocarbamato chelates after extraction from aqueous solution
Summary Small amounts of Ni, Cu and Zn in aqueous solutions can be determined by gas chromatography after extraction of their dipropyldithiocarbamatochelates. Working details for the 0.01–1 ppm range are reported. Reproducibility is markedly improved by addition of an inner standard.
Die Untersuchungen wurden in dankenswerter Weise durch Mittel der Deutschen Forschungsgemeinschaft und des Verbands der chemischen Industrie unterstützt. 相似文献
80.
Schmidt EM Gleiter R Rominger F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(8):1814-1822
The synthesis of 1-alkyl and 1-aryl-1-azacyclotetradeca-3,5,10,12-tetraynes was achieved in a stepwise approach. The key intermediate was 1,13-dibromotrideca-2,4,9,11-tetrayne (18). Reaction with methyl- (19 a), ethyl- (19 b), isopropyl- (19 c), n-butyl- (19 d), and tert-butylamine (19 e) as well as aniline (19 f) and p-methoxyaniline (19 g) gave the corresponding 14-membered tetraynes 20 a-20 g. The ring inversion process of 20 b was studied by variable temperature (1)H NMR spectroscopy. From these measurements a value of 10.6 kcal mol(-1) was calculated for DeltaG(not equal). X-ray investigations on single crystals of 20 b, 20 c, and 20 f revealed the axial position for the substituent at each nitrogen atom. For 20 b we encountered the chair conformation, for 20 c both chair and boat conformations, and for 20 f the boat conformation in the solid state. The reaction of 20 c with concentrated HCl in ethanol yielded 2,10-dichloro-6-isopropyl-6-azatricyclo[9.3.0.0(4,8)]tetradeca-1(11),2,4(8),9-tetraene (25 c). Compound 25 c was oxidized by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to 27 c. The structure of the latter was confirmed by X-ray investigations. The reaction of 20 c in aqueous HCl lead to the formation of 10-chloro-2-isopropyl-1,3,4,6,7,8-hexahydro-2H-benzo[g]isoquinolin-9-one (37 c). The structure of 37 c was verified by X-ray studies on single crystals. 相似文献