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61.
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
62.
Dr. Daniel Brodbeck Dr. Sonia Álvarez-Barcia Dr. Jan Meisner Dr. Florian Broghammer Julian Klepp Dr. Delphine Garnier Dr. Wolfgang Frey Prof. Dr. Johannes Kästner Prof. Dr. René Peters 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(6):1515-1524
Asymmetric 1,2-additions of cyanide yield enantioenriched cyanohydrins as versatile chiral building blocks. Next to HCN, volatile organic cyanide sources are usually used. Among them, cyanoformates are more attractive on technical scale than TMSCN for cost reasons, but catalytic productivity is usually lower. Here, the development of a new strategy for cyanations is described, in which this activity disadvantage is overcome. A Lewis acidic Al center cooperates with an aprotic onium moiety within a remarkably robust bifunctional Al–F–salen complex. This allowed for unprecedented turnover numbers of up to 104. DFT studies suggest an unexpected unique trimolecular pathway in which the ammonium bound cyanide attacks the aldehyde, which itself is activated by the carbonyl group of the cyanoformate binding to the Al center. In addition, a novel practical carboxycyanation method was developed that makes use of KCN as the sole cyanide source. The use of a pyrocarbonate as carboxylating reagent provided the best results. 相似文献
63.
We assume that both the concurrence Cr of a two-rebits state and the concurrence Cq of the usual two-qubits states are represented by hermitian operators (observables). We calculate the respective uncertainty ΔCr and the uncertainty ΔCq measured both as the standard deviation . We make the strictly mathematical assumption that there exists a canonical conjugate variable (called ξ) to the concurrence (C) such that both quantities satisfy a Robertson’s [1] uncertainty inequality of the form \( {\left(\Delta A\right)}^2{\left(\Delta B\right)}^2>{\left|\frac{1}{2}\left\langle \right[A,B\left]\right\rangle \right|}^2 \). From such inequality we impose bounds for both uncertainties Δξr and Δξq.
相似文献64.
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
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Vanessa F. M. Carvalho Daniela V. Giacone Leticia V. Costa‐Lotufo Edilberto Rocha Silveira Luciana B. Lopes 《Biomedical chromatography : BMC》2019,33(2)
This study reports the development of a simple and reproducible method, with high rates of recovery, to extract the cytotoxic agent piplartine from skin layers, and a sensitive and rapid UV‐HPLC method for its quantification. Considering the potential of piplartine for topical treatment of skin cancer, this method may find application for formulation development and pharmacokinetics studies to assess cutaneous bioavailability. Porcine skin was employed as a model for human tissue. Piplartine was extracted from the stratum corneum (SC) and remaining viable skin layers (VS) using methanol, vortex homogenization and bath sonication, and subsequently assayed by HPLC using a C18 column, and 1:1 (v/v) acetonitrile–water (adjusted to pH 4.0 with acetic acid 0.1%) as mobile phase. The quantification limit of piplartine was 0.2 μg/mL (0.6 μm ), and the assay was linear up to 5 μg/mL (15.8 μm ), with within‐day and between‐days assay coefficients of variation and relative errors <15%. Piplartine recovery from SC and VS varied from 86 to 96%. The method was suitable to assay samples from skin penetration studies, enabling detection of differences in cutaneous delivery in different skin compartments resulting from treatment with various formulations and time periods. 相似文献
68.
Synchronizing Substrate Activation Rates in Multicomponent Reactions with Metal–Organic Framework Catalysts 下载免费PDF全文
Dr. Lina María Aguirre‐Díaz Dr. Marta Iglesias Dr. Natalia Snejko Prof. Enrique Gutiérrez‐Puebla Prof. M. Ángeles Monge 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(19):6654-6665
A study on the influence of the cation coordination number, number of Lewis acid centers, concurrent existence of Lewis base sites, and structure topology on the catalytic activity of six new indium MOFs, has been carried out for multicomponent reactions (MCRs). The new indium polymeric frameworks, namely [In8(OH)6(popha)6(H2O)4]?3 H2O ( InPF‐16 ), [In(popha)(2,2′‐bipy)]?3 H2O ( InPF‐17 ), [In3(OH)3(popha)2(4,4′‐bipy)]?4 H2O ( InPF‐18 ), [In2(popha)2(4,4′‐bipy)2]?3 H2O ( InPF‐19 ), [In(OH)(Hpopha)]?0.5 (1,7‐phen) ( InPF‐20 ), and [In(popha)(1,10‐phen)]?4 H2O ( InPF‐21 ) (InPF=indium polymeric framework, H3popha=5‐(4‐carboxy‐2‐nitrophenoxy)isophthalic acid, phen=phenanthroline, bipy=bipyridine), have been hydrothermally obtained by using both conventional heating (CH) and microwave (MW) procedures. These indium frameworks show efficient Lewis acid behavior for the solvent‐free cyanosilylation of carbonyl compounds, the one pot Passerini 3‐component (P‐3CR) and the Ugi 4‐component (U‐4CR) reactions. In addition, InPF‐17 was found to be a highly reactive, recyclable, and environmentally benign catalyst, which allows the efficient synthesis of α‐aminoacyl amides. The relationship between the Lewis base/acid active site and the catalytic performance is explained by the 2D seven‐coordinated indium framework of the catalyst InPF‐17 . This study is an attempt to highlight the main structural and synthetic factors that have to be taken into account when planning a new, effective MOF‐based heterogeneous catalyst for multicomponent reactions. 相似文献
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J.C.S. Rocha B.V. Costa P.Z. Coura S.A. Leonel R.A. Dias 《Journal of magnetism and magnetic materials》2012
In this work we report a numerical Monte Carlo study of the behavior of a magnetic nano-disk put over an antiferromagnetic substrate. Three approaches were considered for describe the substrate: (1) A stacked antiferromagnetic configuration, (2) an Ising like arrangement and (3) Heisenberg like spins. For the Heisenberg case we still have considered an easy-plane and an easy-axis symmetry of the substrate. The hysteresis loop for the nano-disk is obtained by considering the three cases. The signature of the vortex in the nano-disk appears as small jumps in the hysteresis curve. Exchange bias effects are observed since the substrate has an easy axis symmetry. 相似文献