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排序方式: 共有644条查询结果,搜索用时 78 毫秒
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Dr. Abdessamad Grirrane Dr. Eleuterio Álvarez Prof. Dr. Hermenegildo García Prof. Dr. Avelino Corma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(40):8810-8818
The cationic complex [(JohnPhos–Au)3(acetylide)][SbF6] (JohnPhos=(2-biphenyl)di-tert-butylphosphine, L1) has been characterised structurally and features an acetylide–trigold(I)–JohnPhos system; the trinuclear–acetylide unit, coordinated to the monodentate bulk phosphines, adopts an unprecedented μ,η1,η2,η1 coordination mode with an additional interaction between distal phenyl rings and gold centres. Other cationic σ,π-[(gold(I)L1)2] complexes have also been isolated. The reaction of trimethylsilylacetylene with various alcohols (iPrOH, nBuOH, n-HexOH) catalysed by cationic [AuIL1][SbF6] complexes in CH2Cl2 at 50 °C led to the formation of acetaldehyde acetals with a high degree of chemo- and regioselectivity. The reaction mechanism was studied, and several organic and inorganic intermediates have been characterised. A comparative study with the analogous cationic [CuIL1][PF6] complex revealed different behaviour; the copper metal is lost from the coordination sphere leading to the formation of cationic vinylphosphonium and copper nanoparticles. Additionally, a new catalytic approach for the formation of this high-value cationic vinylphosphonium has been established. 相似文献
3.
Prof. Dr. Javier A. Cabeza Dr. Israel Fernández Dr. José M. Fernández-Colinas Dr. Pablo García-Álvarez Carlos J. Laglera-Gándara 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(53):12423-12430
An efficient synthesis of 2-di-tert-butylphosphanylmethylpyrrole (HpyrmPtBu2), by treating 2-dimethylaminomethylpyrrole (HpyrmNMe2) with tBu2PH at 135 °C in the absence of any solvent, has allowed the preparation of the new PGeP germylene Ge(pyrmPtBu2)2 ( 1 ), by treating [GeCl2(dioxane)] with LipyrmPtBu2, in which the Ge atom is stabilized by intramolecular interactions with one (solid state) or both (solution) of its phosphane groups. Reactions of germylene 1 with Group 10 metal dichlorido complexes containing easily displaceable ligands have led to [MCl{κ3P,Ge,P-GeCl(pyrmPtBu2)2}] [M=Ni ( 2 ), Pd ( 3 ), Pt ( 4 )], which have an unflawed square-planar metal environment. Treatment of germylene 1 with [AuCl(tht)] (tht=tetrahydrothiophene) rendered [Au{κ3P,Ge,P-GeCl(pyrmPtBu2)2}] ( 5 ), which is a rare case of a T-shaped gold(I) complex. The hydrolysis of 5 gave the linear gold(I) derivative [Au(κP-HpyrmPtBu2)2]Cl ( 6 ). Complexes 2 – 5 contain a PGeP pincer chloridogermyl ligand that arises from the insertion of the Ge atom of germylene 1 into a M−Cl bond of the corresponding metal reagent. The bonding in these molecules has been studied by DFT/NBO/QTAIM calculations. These results demonstrate that the great flexibility of germylene 1 makes it a better precursor to PGeP pincer complexes than the previously known germylenes of this type. 相似文献
4.
Prof. Dr. Javier A. Cabeza Dr. Pablo García-Álvarez Prof. Dr. Mar Gómez-Gallego Laura González-Álvarez Alba D. Merinero Prof. Dr. Miguel A. Sierra 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(36):8635-8642
The reactivity of amidinatotetrylenes of the type E(tBu2bzm)R1 (E=Si, Ge; tBu2bzm=N,N′-bis(tertbutyl)benzamidinate; R1=alkyl or aryl) with the chromium Fischer alkynylcarbene complexes [Cr{C(OEt)C2R2}(CO)5] (R2=Ph; ferrocenyl, Fc) has been studied. At room temperature, two different reaction pathways have been identified: (a) attack of the amidinatotetrylene to the alkynyl C2 atom (γ-attack), which leads to σ-allenyl complexes in which the original Ccarbene atom maintains its attachment to the Cr(CO)5 and OEt groups (compounds 3 ), and (b) attack of the amidinatotetrylene to the Ccarbene atom (α-attack), which ends in σ-allenyl complexes in which the original Ccarbene atom is not attached to the metal atom and has been inserted into an E−N bond of the amidinatotetrylene forming an E-C-N-C-N five-membered ring (compounds 4 ). It has been found that compounds 3 are thermodynamically less stable than their corresponding 4 isomers and that some of the former (E=Ge; R1=CH2SiMe3) can be transformed into the latter upon heating. At high temperatures (>70 °C) the reactions involving bulky amidinatotetrylenes (R1=Mes, tBu) end in the carbene-substitution products [Cr{E(tBu2bzm)R1}(CO)5]. 相似文献
5.
Dr. Paula Gómez‐Álvarez Prof. Sofia Calero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(52):18705-18708
The separation of carbon dioxide from flue gas is essential for the reduction of greenhouse gas emissions. In adsorptive methods, the challenge lies in the choice of suitable porous materials. Among all zeolite topologies, a number of adsorbents with pore dimensions in the range of the guest molecules were identified to allow an excellent separation by diffusion, and MRE and AFO zeolite topologies appear to be the best candidates based on equilibrium adsorption. Also, it was found that the behavior of this gas mixture in DFT and APD zeolites differed from the normal behavior. 相似文献
6.
Claudia González de Vega Cesar Álvarez Llamas Nerea Bordel Rosario Pereiro Alfredo Sanz-Medel 《Analytica chimica acta》2015
The analytical capabilities of a glow discharge (GD) as a secondary source for excitation/ionization of the material provided by laser ablation (LA) have been compared to conventional laser induced breakdown spectroscopy (LIBS). In LA–GD both sources can be independently adjusted to optimize the sampling process and then its subsequent excitation. This could involve a number of analytical performance advantages, such as reduced matrix dependence, greater precision and sensitivity than those encountered in LIBS. For such purpose, an ablation chamber design including two electrodes to generate the GD discharge has been built and assayed. A comparison between LIBS and LA–GD–OES has been carried out, both, under reduced argon and helium atmospheres. Different sets of samples (conducting reference materials, glass and fluorine pellets) have been used to evaluate the novel coupled technique. The LA–GD coupled system has shown to provide lower detection limits. In addition, best linear correlations between intensities and concentrations and lower matrix effects have also been found using the coupled system. Moreover, special advantages of the LA–GD–OES have also been demonstrated for the analysis of fluorine. 相似文献
7.
Teresa Álvarez 《Mathematical Methods in the Applied Sciences》2015,38(9):1838-1846
A classical formula for the gap between two densely defined closed operators in a Hilbert space is extended to the case of linear relations. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
8.
Dihydrogen Catalysis of the Reversible Formation and Cleavage of CH and NH Bonds of Aminopyridinate Ligands Bound to (η5‐C5Me5)IrIII 下载免费PDF全文
Dr. Ana Zamorano Dr. Nuria Rendón Dr. Joaquín López‐Serrano Dr. José E. V. Valpuesta Dr. Eleuterio Álvarez Prof. Dr. Ernesto Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2576-2587
This study focuses on a series of cationic complexes of iridium that contain aminopyridinate (Ap) ligands bound to an (η5‐C5Me5)IrIII fragment. The new complexes have the chemical composition [Ir(Ap)(η5‐C5Me5)]+, exist in the form of two isomers ( 1+ and 2+ ) and were isolated as salts of the BArF? anion (BArF=B[3,5‐(CF3)2C6H3]4). Four Ap ligands that differ in the nature of their bulky aryl substituents at the amido nitrogen atom and pyridinic ring were employed. In the presence of H2, the electrophilicity of the IrIII centre of these complexes allows for a reversible prototropic rearrangement that changes the nature and coordination mode of the aminopyridinate ligand between the well‐known κ2‐N,N′‐bidentate binding in 1+ and the unprecedented κ‐N,η3‐pseudo‐allyl‐coordination mode in isomers 2+ through activation of a benzylic C?H bond and formal proton transfer to the amido nitrogen atom. Experimental and computational studies evidence that the overall rearrangement, which entails reversible formation and cleavage of H?H, C?H and N?H bonds, is catalysed by dihydrogen under homogeneous conditions. 相似文献
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Experimental and Computational Studies of the Molybdenum‐Flanking Arene Interaction in Quadruply Bonded Dimolybdenum Complexes with Terphenyl Ligands 下载免费PDF全文
Dr. Mario Carrasco Irene Mendoza Dr. Eleuterio Álvarez Dr. Abdessamad Grirrane Dr. Celia Maya Dr. Riccardo Peloso Dr. Amor Rodríguez Andrés Falceto Prof. Dr. Santiago Álvarez Prof. Dr. Ernesto Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):410-421
To clarify the nature of the Mo?Carene interaction in terphenyl complexes with quadruple Mo?Mo bonds, ether adducts of composition [Mo2(Ar′)(I)(O2CR)2(OEt2)] have been prepared and characterized (Ar′=ArXyl2, R=Me; Ar′=ArMes2, R=Me; Ar′=ArXyl2, R=CF3) (Mes=mesityl; Xyl=2,6‐Me2C6H3, from now on xylyl) and their reactivity toward different neutral Lewis bases investigated. PMe3, P(OMe)3 and PiPr3 were chosen as P‐donors and the reactivity studies complemented with the use of the C‐donors CNXyl and CN2C2Me4 (1,3,4,5‐tetramethylimidazol‐2‐ylidene). New compounds of general formula [Mo2(Ar′)(I)(O2CR)2( L )] were obtained, except for the imidazol‐2‐ylidene ligand that yielded a salt‐like compound of composition [Mo2(ArXyl2)(O2CMe)2(CN2C2Me4)2]I. The Mo?Carene interaction in these complexes has been analyzed with the aid of X‐ray data and computational studies. This interaction compensates the coordinative and electronic unsaturation of one of the Mo atoms in the above complexes, but it seems to be weak in terms of sharing of electron density between the Mo and Carene atoms and appears to have no appreciable effect in the length of the Mo?Mo, Mo?X, and Mo? L bonds present in these molecules. 相似文献