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排序方式: 共有120条查询结果,搜索用时 31 毫秒
1.
Breher F Rüegger H Mlakar M Rudolph M Deblon S Schönberg H Boulmaâz S Thomaier J Grützmacher H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):641-653
The formation of adducts of the square-planar 16-electron complexes trans-[M(tropp(ph))(2)](+) and cis-[M(tropp(ph))(2)](+) (M=Rh, Ir; tropp(Ph)=5-diphenylphosphanyldibenzo[a,d]cycloheptene) with acetonitrile (acn) and Cl(-), and the redox chemistry of these complexes was investigated by various physical methods (NMR and UV-visible spectroscopy, square-wave voltammetry), in order to obtain some fundamental thermodynamic and kinetic data for these systems. A trans/cis isomerization cannot be detected for [M(tropp(ph))(2)](+) in non-coordinating solvents. However, both isomers are connected through equilibria of the type trans-[M(tropp(ph))(2)](+)+L<==>[ML(tropp(ph))(2)](n)<==>cis-[M(tropp(ph))(2)](+)+L, involving five-coordinate intermediates [ML(tropp(ph))(2)](n) (L=acn, n=+1; L=Cl(-), n=0). Values for K(d) (K(f)), that is, the dissociation (formation) equilibrium constant, and k(d) (k(f)), that is, the dissociation (formation) rate constant, were obtained. The formation reactions are fast, especially with the trans isomers (k(f)>1x10(5) m(-1) s(-1)). The reaction with the sterically more hindered cis isomers is at least one order of magnitude slower. The stability of the five-coordinate complexes [ML(tropp(ph))(2)](n) increases with Ir>Rh and Cl(-)>acn. The dissociation reaction has a pronounced influence on the square-wave (SW) voltammograms of trans/cis-[Ir(tropp(ph))(2)](+). With the help of the thermodynamic and kinetic data independently determined by other physical means, these reactions could be simulated and allowed the setting up of a reaction sequence. Examination of the data obtained showed that the trans/cis isomerization is a process with a low activation barrier for the four-coordinate 17-electron complexes [M(tropp(ph))(2)](0) and especially that a disproportionation reaction 2 trans/cis-[M(tropp(ph))(2)](0)-->[M(tropp(ph))(2)](+)+[M(tropp(ph))(2)](-) may be sufficiently fast to mask the true reactivity of the paramagnetic species, which are probably less reactive than their diamagnetic equilibrium partners. 相似文献
2.
Summary The effects of pH, gas flow rate and collector concentration on the rate of thorium removal by foaming with sodium lauryl sulphate have been investigated. The obtained data indicate that only aged hydrated thorium oxide is removed by a flotation mechanism. All the other colloidal and condensed thorium species as well as the colloidal sublates which are formed between the dissolved thorium species and the collector anions appear to be removed by partition and their removal rates could be described by a reversible first-order rate equation. The obtained results are discussed in terms of thorium hydrolysis.
With 7 figures 相似文献
Zusammenfassung Der Einfluß der pH-Werte, Gasdurchflußmengen und Kollektor-Konzentration auf die Geschwindigkeit der Entfernung des Thoriums durch Schaumbildung mit Natrium-Lauryl-Sulfat wurde untersucht. Die Ergebnisse zeigen, daß das gealterte, wässerige Thoriumoxid durch Flotations-Mechanismen entfernt wird. Die anderen kolloidalen und kondensierten Thorium-Spezien und auch die Kolloidalprodukte, die durch Reaktionen zwischen den gelösten Thoriumspezien und den Kollektor-Anionen formiert sind, sind durch die Verteilung entfernt worden. Die Entfernungsgeschwindigkeit kann beschrieben werden durch eine reversible 1. Ordnungs-Gleichung. Die Ergebnisse werden in Abhängigkeit einer ThoriumHydrolyse diskutiert.
With 7 figures 相似文献
3.
Aloui M Chambers DJ Cumpstey I Fairbanks AJ Redgrave AJ Seward CM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(11):2608-2621
The technique of intramolecular aglycon delivery (IAD), whereby a glycosyl acceptor is temporarily appended to a hydroxyl group of a glycosyl donor is an attractive method that can allow the synthesis of 1,2-cis glycosides in an entirely stereoselective fashion. 2-O-Allyl protected thioglycoside donors are excellent substrates for IAD, and may be glycosylated stereoselectively through a three-step reaction sequence. This sequence consists of quantitative yielding allyl bond isomerisation, to produce vinyl ethers that can then undergo N-iodosuccinimide mediated tethering of the desired glycosyl acceptor, and subsequent intramolecular glycosylation, to yield either alpha-glucosides or beta-mannosides accordingly. Although attempted one-pot tethering and glycosylation is hampered by competitive intermolecular reaction with excess glycosyl acceptor, this problem can be simply overcome by the use of excess glycosyl donor. Allyl mediated IAD is a widely applicable practical alternative to other IAD approaches for the synthesis of beta-mannosides, that is equally applicable for alpha-gluco linkages. It is advantageous in terms of both simplicity of application and yield, and in addition has no requirement for cyclic 4,6-protection of the glycosyl donor. 相似文献
4.
The Ramanujan Journal - Let $$s_{q}$$ denote the sum of digits function in base q. The aim of this work is to estimate the exponential sums involving the sum of digits of shifted integers, namely... 相似文献
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6.
Souilah Mohammed Hachi Mohamed Fitri Asmae Benjelloun Adil Touimi El Khattabi Souad Benzakour Mohammed Mcharfi Mohammed Zgou Hsaine 《Research on Chemical Intermediates》2021,47(2):875-893
Research on Chemical Intermediates - A series of D–π–A architectures dyes with Coumarin-based derivatives as difluorenylaminocoumarin (DF) and diphenylaminocoumarin (DP) have been... 相似文献
7.
Amel Souibgui Anne Gaucher Jérôme Marrot Flavien Bourdreux Faouzi Aloui Béchir Ben Hassine Damien Prim 《Tetrahedron》2014
New series of acridines and phenanthrolines have been prepared from β-chlorovinyl aldehydes and various aniline derivatives allowing the installation of valuable substituents, such as ketone, nitro or amino groups at the heterocyclic core. X-ray analyses confirmed the structures of acridines and phenanthrolines as well as the presence of partially hydrogenated rings and their crucial impact on the overall shape of the acridine-based architectures. 1H NMR revealed the helical behaviour of several acridine motives. Comparison of UV data between architectures and influence of number of partially hydrogenated rings is also described. 相似文献
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9.
Ziyat Hamid Elmzioui Souad Naciri Bennani Mohammed Houssaini Jamal Allaoui Safae Arhzaf Said 《Research on Chemical Intermediates》2021,47(6):2605-2627
Research on Chemical Intermediates - The objective of this work is to test the effectiveness of hydrotalcite as an adsorbent for the retention of nitrate and nitrite ions and to study the influence... 相似文献
10.
Bazzi Aicha Abbiche Khalid Izzaouihda Safia Acharjee Nivedita Zejli Hanane Marakchi Khadija Komiha Najia El Issami Souad Bazzi Lahcen Hilali Mustapha 《Structural chemistry》2021,32(6):2183-2198
Structural Chemistry - A combined experimental and theoretical study is presented to predict and analyze the inhibition efficiency and adsorption mechanism of 4-aminobenzoic acid molecule for... 相似文献