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931.
Cyclic gamma-silyloxy-beta-hydroxy-alpha-diazoesters undergo efficient rupture of the Cbeta-Cgamma bond when treated with tin tetrachloride to provide tethered aldehyde ynoate products in high yield. 相似文献
932.
Rhenium carbonyl compounds with (diphenyl)phosphinoalkynes and a sterically hindered phosphinoalkyne
The synthesis and characterization of two series of rhenium carbonyl complexes with P-coordinated phosphinoalkynes are reported. The anionic fac-[ReBr2(CO)3(Ph2PCCR)]− and neutral fac-[ReBr(CO)3(Ph2PCCR)2] (R = Ph, Tol, tBu) complexes have been prepared and the crystal structures of fac-[ReBr2(CO)3(Ph2PCCTol)]− and fac-[ReBr(CO)3(Ph2PCCtBu)2] have been determined by X-ray crystallography, evidencing the presence of the uncoordinated alkyne in all these compounds. The phosphinoalkyne (o-Tol)2PCCPh with bulky groups linked to the phosphorus atom was prepared in order to avoid the coordination of two phosphinoalkynes in cis-position around the rhenium metal. As a result, surprisingly the complex fac-[ReBr(CO)3{(o-Tol)2PCCPh}2] was obtained. The crystal structure of this compound was determined confirming the cis-coordination of two bulky phosphinoalkynes in an octahedral rhenium atom. The electronic properties of the uncoordinated alkyne in these new rhenium complexes was analyzed, based on 13C NMR data and was compared with reported data on iron complexes. The results obtained indicate that the electronic characteristics of uncoordinated alkynes are similar in both families of complexes. Thus, the different reactivity observed between rhenium and iron complexes is related to the different nature of metallic fragments rather than to electronic features of uncoordinated alkynes. 相似文献
933.
Hessel Cristian Perini Nickson Sitta Elton 《Journal of Solid State Electrochemistry》2023,27(3):705-714
Journal of Solid State Electrochemistry - The cadmium sulfide (CdS) is one of the most applied chalcogenides to the water splitting (WS) on photoelectrochemical cells (PEC). The CdS bandgap is... 相似文献
934.
In recent years, 3D printing of carbon-based conductive filaments has received growing attention for assembling electrodes to be used in a wide variety of electroanalytical devices and applications. Despite the large amount of work present in literature concerning the development of three-dimensional (3D) conductive structures, its potential as dry deposition method for assembling two-dimensional (2D) electrodes to be used in planar configuration is still largely unexplored. In fact, the possibility to rapidly change the geometry of the electrochemical circuits, associated with the reduction of waste and the absence of solvents, which are instead important components of ink and paste formulations, makes this strategy a valid green and efficient alternative to other deposition approaches such as screen-printing technology. We report here a rapid and solvent-free method for assembling fully 3D printed flexible planar electroanalytical platforms (3DEPs) to be used with microliters of liquid. At the same time, a novel protocol for the surface pre-treatment of 3D printed electrodes based on ultrasonication in aqueous NaOH solution followed by electrochemical activation using the same medium, is presented. In addition, the same procedure has proved to be efficient for cleaning the electrode surface after electrochemical passivation, thus confirming the validity of both time-efficient and environmentally-friendly assembling and activation/cleaning procedures developed which allow efficient and reusable electrodes to be produced. Finally, 3DEPs were tested by a proof-of-concept quantification of a commonly used food dye (Brilliant Blue, E-133) in commercial solutions used for homemade food coloring. 相似文献
935.
936.
Wiedenbeck M Kasemset B Kasper M 《Rapid communications in mass spectrometry : RCM》2008,22(5):623-629
We describe a novel mass filtering concept based on the acceleration of a pulsed ion beam through a stack of electrostatic plates. A precisely controlled traveling wave generated within such an ion guide will induce a mass-selective ion acceleration, with mass separation ultimately accomplished via a simple energy-filtering system. Crucial for successful filtering is that the velocity with which the traveling wave passes through the ion guide must be dynamically controlled in order to accommodate the acceleration of the target ion species. Mass selection is determined by the velocity and acceleration with which the wave traverses the ion guide, whereby the target species will acquire a higher kinetic energy than all other lighter as well as heaver species. Finite element simulations of this design demonstrate that for small masses a mass resolution M/DeltaM approximately 1000 can be achieved within an electrode stack containing as few as 20 plates. Some of the possible advantages and drawbacks which distinguish this concept from established mass spectrometric technologies are discussed. 相似文献
937.
Chemoselective transfer hydrogenation to nitroarenes mediated by cubane-type Mo3S4 cluster catalysts
Sorribes I Wienhöfer G Vicent C Junge K Llusar R Beller M 《Angewandte Chemie (International ed. in English)》2012,51(31):7794-7798
Chemoselective cubes: Cubane-type [Mo(3)S(4)X(3)(dmpe)(3)](+) clusters (dmpe = 1,2-(bis)dimethylphosphinoethane), in combination with an azeotropic 5:2 mixture of HCOOH and NEt(3) as the reducing agent, act as selective cluster catalysts (X = H) or precatalysts (X = Cl) for the transfer hydrogenation of functionalized nitroarenes, without the formation of hazardous hydroxylamines. 相似文献
938.
Bellarosa L Díez J Gimeno J Lledós A Suárez FJ Ujaque G Vicent C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(25):7749-7765
The catalytic activity of ruthenium(IV) ([Ru(η(3):η(3)-C(10)H(16))Cl(2)L]; C(10)H(16) = 2,7-dimethylocta-2,6-diene-1,8-diyl, L = pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole, 2-(1H-pyrazol-3-yl)phenol or indazole) and ruthenium(II) complexes ([Ru(η(6)-arene)Cl(2)(3,5-dimethylpyrazole)]; arene = C(6)H(6), p-cymene or C(6)Me(6)) in the redox isomerisation of allylic alcohols into carbonyl compounds in water is reported. The former show much higher catalytic activity than ruthenium(II) complexes. In particular, a variety of allylic alcohols have been quantitatively isomerised by using [Ru(η(3):η(3)-C(10)H(16))Cl(2)(pyrazole)] as a catalyst; the reactions proceeded faster in water than in THF, and in the absence of base. The isomerisations of monosubstituted alcohols take place rapidly (10-60?min, turn-over frequency = 750-3000?h(-1)) and, in some cases, at 35?°C in 60?min. The nature of the aqueous species formed in water by this complex has been analysed by ESI-MS. To analyse how an aqueous medium can influence the mechanism of the bifunctional catalytic process, DFT calculations (B3LYP) including one or two explicit water molecules and using the polarisable continuum model have been carried out and provide a valuable insight into the role of water on the activity of the bifunctional catalyst. Several mechanisms have been considered and imply the formation of aqua complexes and their deprotonated species generated from [Ru(η(3):η(3)-C(10)H(16))Cl(2)(pyrazole)]. Different competitive pathways based on outer-sphere mechanisms, which imply hydrogen-transfer processes, have been analysed. The overall isomerisation implies two hydrogen-transfer steps from the substrate to the catalyst and subsequent transfer back to the substrate. In addition to the conventional Noyori outer-sphere mechanism, which involves the pyrazolide ligand, a new mechanism with a hydroxopyrazole complex as the active species can be at work in water. The possibility of formation of an enol, which isomerises easily to the keto form in water, also contributes to the efficiency in water. 相似文献
939.
Cristian D. EneAndreea Lungu Constantin Mihailciuc Mihaela Hillebrand Catalina Ruiz-PérezMarius Andruh 《Polyhedron》2012,31(1):539-547
The crystal structures of two pentacyanido(L) ferrate(III) complexes, [P(C6H5)4]2[Fe(CN)5(prz)]·4H2O 1, [P(C6H5)4]2[Fe(CN)5(4,4′-bipy)]·3H2O 2, have been solved. Within the two complex anions the iron atoms are hexacoordinated by five cyanido ligands, the sixth position being occupied by the nitrogen atom arising from pyrazine and, respectively, 4,4′-bipyridine. The electrochemical properties of compounds 1, 2 and of the azido derivative, (Ph4As)2[Na(H2O)4][Fe(CN)5(N3)] 3, have been investigated by cyclic voltammetry. A relatively complicated redox behavior of these complexes was found, due especially to the electron transfer involving the central metallic ion that changes reversibly its oxidation state (FeIII/FeII redox site) and also to the coligand (4,4′-bipyridine, pyrazine or azide) which intervenes in a distinct electron transfer. The experimental data have been rationalized through DFT calculations. 相似文献
940.
Dr. Luca Bellarosa Dr. Josefina Díez Prof. Dr. José Gimeno Prof. Dr. Agustí Lledós Francisco J. Suárez Dr. Gregori Ujaque Dr. Cristian Vicent 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(25):7749-7765
The catalytic activity of ruthenium(IV) ([Ru(η3:η3‐C10H16)Cl2L]; C10H16=2,7‐dimethylocta‐2,6‐diene‐1,8‐diyl, L=pyrazole, 3‐methylpyrazole, 3,5‐dimethylpyrazole, 3‐methyl‐5‐phenylpyrazole, 2‐(1H‐pyrazol‐3‐yl)phenol or indazole) and ruthenium(II) complexes ([Ru(η6‐arene)Cl2(3,5‐dimethylpyrazole)]; arene=C6H6, p‐cymene or C6Me6) in the redox isomerisation of allylic alcohols into carbonyl compounds in water is reported. The former show much higher catalytic activity than ruthenium(II) complexes. In particular, a variety of allylic alcohols have been quantitatively isomerised by using [Ru(η3:η3‐C10H16)Cl2(pyrazole)] as a catalyst; the reactions proceeded faster in water than in THF, and in the absence of base. The isomerisations of monosubstituted alcohols take place rapidly (10–60 min, turn‐over frequency=750–3000 h?1) and, in some cases, at 35 °C in 60 min. The nature of the aqueous species formed in water by this complex has been analysed by ESI‐MS. To analyse how an aqueous medium can influence the mechanism of the bifunctional catalytic process, DFT calculations (B3LYP) including one or two explicit water molecules and using the polarisable continuum model have been carried out and provide a valuable insight into the role of water on the activity of the bifunctional catalyst. Several mechanisms have been considered and imply the formation of aqua complexes and their deprotonated species generated from [Ru(η3:η3‐C10H16)Cl2(pyrazole)]. Different competitive pathways based on outer‐sphere mechanisms, which imply hydrogen‐transfer processes, have been analysed. The overall isomerisation implies two hydrogen‐transfer steps from the substrate to the catalyst and subsequent transfer back to the substrate. In addition to the conventional Noyori outer‐sphere mechanism, which involves the pyrazolide ligand, a new mechanism with a hydroxopyrazole complex as the active species can be at work in water. The possibility of formation of an enol, which isomerises easily to the keto form in water, also contributes to the efficiency in water. 相似文献