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Frontispiece: Combined Spectroscopic and Electrochemical Detection of a NiI⋅⋅⋅HN Bonding Interaction with Relevance to Electrocatalytic H2 Production 下载免费PDF全文
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Dr. Martin Piesch Dr. Amélie Nicolay Dr. Maria Haimerl Dr. Michael Seidl Dr. Gábor Balázs Prof. T. Don Tilley Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(45):e202201144
The bridging MeCN ligand in the dicopper(I) complexes [(DPFN)Cu2(μ,η1 : η1-MeCN)][X]2 (X=weakly coordinating anion, NTf2 ( 1 a ), FAl[OC6F10(C6F5)]3 ( 1 b ), Al[OC(CF3)3]4 ( 1 c )) was replaced by white phosphorus (P4) or yellow arsenic (As4) to yield [(DPFN)Cu2(μ,η2 : η2-E4)][X]2 (E=P ( 2 a – c ), As ( 3 a – c )). The molecular structures in the solid state reveal novel coordination modes for E4 tetrahedra bonded to coinage metal ions. Experimental data and quantum chemical computations provide information concerning perturbations to the bonding in coordinated E4 tetrahedra. Reactions with N-heterocyclic carbenes (NHCs) led to replacement of the E4 tetrahedra with release of P4 or As4 and formation of [(DPFN)Cu2(μ,η1 : η1-MeNHC)][X]2 ( 4 a,b ) or to an opening of one E−E bond leading to an unusual E4 butterfly structural motif in [(DPFN)Cu2(μ,η1 : η1-E4DippNHC)][X]2 (E=P ( 5 a,b ), E=As ( 6 )). With a cyclic alkyl amino carbene (EtCAAC), cleavage of two As−As bonds was observed to give two isomers of [(DPFN)Cu2(μ,η2 : η2-As4EtCAAC)][X]2 ( 7 a,b ) with an unusual As4-triangle+1 unit. 相似文献
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Roberto Morales-Cerrada Dr. Christophe Fliedel Dr. Jean-Claude Daran Dr. Florence Gayet Dr. Vincent Ladmiral Dr. Bruno Améduri Prof. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):296-308
Thermal decarbonylation of the acyl compounds [Mn(CO)5(CORF)] (RF=CF3, CHF2, CH2CF3, CF2CH3) yielded the corresponding alkyl derivatives [Mn(CO)5(RF)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(12CO)4(eq-13CO)(RF)] and [Mn(12CO)4(ax-13CO)(RF)] isotopomers and a ranking of the RF donor power in the order CF3<CHF2<CH2CF3≈CF2CH3. The homolytic Mn−RF bond cleavage in [Mn(CO)5(RF)] at various temperatures under saturation conditions with trapping of the generated RF radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH≠ and ΔS≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−RF bond cleavage was further demonstrated by the observation that [Mn(CO)5(CF3)] (the compound with the strongest Mn−RF bond) initiated the radical polymerization of vinylidene fluoride (CH2=CF2) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation. 相似文献
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Palladium‐Catalyzed Regioselective C‐Benzylation via a Rearrangement Reaction: Access to Benzyl‐Substituted Anilines 下载免费PDF全文
Dr. Manuel Amézquita‐Valencia Prof. Howard Alper 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(47):16774-16778
An unprecedented C‐benzylation rearrangement reaction, catalyzed by palladium, is reported. The reaction proceeds by rearrangement leading to the direct synthesis of para or ortho benzyl‐substituted N‐methylanilines. The product is obtained in high regioselectivity, without the need to use a ligand for the catalytic process. 相似文献
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M. Amélia Santos Sérgio M. Marques Sílvia Chaves 《Coordination chemistry reviews》2012,256(1-2):240-259
Hydroxypyridinones (HPs) are a family of N-heterocyclic core chelators which, based on their specific metal-coordination, easy manipulation/derivatization and biocompatibility, have been an attractive target for the development of new pharmaceutical drugs with manifold uses. Herein we describe the most recent advances reported in the literature on HPs, with a special focus on the metal chelating properties of the 3-hydroxy-4-pyridinone (3,4-HP) derivatives, and the different approaches used to functionalize these chelators to improve their biological properties, namely in terms of bioavailability and specific bio-targeting abilities. Representative examples of HPs are included, mostly for applications as chelating drugs for sequestration or passivation of metal overload or deregulated biometals, but also as metallodrugs for potential diagnostic/therapeutic purposes. These examples are discussed in terms of the chelating properties and structure–activity relationships. 相似文献
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M. Amélia Santos Adelino Afonso M. Matilde Marques Craig Wilcox 《Supramolecular chemistry》2013,25(3):201-215
Abstract New receptors based upon a carboxamidonaphthyridine unit derivatized with the polyaromatic segments [4-(1-pyrenyl)butyroylamino] and [3-(9-anthracenyl)propanoylamino] have been synthesized and studied by 1H NMR titration in their binding interaction to the guanosine-C8 adducts from the carcinogens 2-acetylaminofluorene and 2-aminofluorene. The high binding energy, in comparison with that of the non-derivatized analogues, is rationalized in terms of a bi-site interaction (hydrogen bonding and aromatic stacking). Although many factors may contribute to the strength of the host-guest complexes described herein, it appears that in some cases π-π interaction may induce a concomitant bending in the hydrogen bond system. 相似文献
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Joana Sousa Gilberto Alves Ana Fortuna Angelina Pena Celeste Lino Amílcar Falcão 《Biomedical chromatography : BMC》2011,25(5):535-541
A simple and fast liquid chromatographic method coupled with fluorescence detection (LC‐FD) is reported, for the first time, for the simultaneous quantification of norfloxacin (NOR), ciprofloxacin (CIP) and lomefloxacin (LOM) in human plasma, using levofloxacin as internal standard (IS). Sample preparation consists of a single‐step precipitation of plasma proteins followed by vortex‐mixing and centrifugation. Chromatographic separation was achieved within 7 min on a reversed‐phase C18 column with a mobile phase consisting of 0.1% aqueous formic acid (pH = 3.0, triethylamine)–methanol (82:18, v/v) pumped isocratically at 1.2 mL/min. The detector was set at excitation/emission wavelengths of 278/450 nm. Calibration curves were linear (r2 ≥ 0.994) in the range of 0.02–5.0 µg/mL, and the limit of quantification was established at 0.02 µg/mL for all analytes (NOR, CIP and LOM). The overall precision did not exceed 8.19% and accuracy was within ±10.91%. NOR, CIP and LOM were extracted from human plasma with an overall mean recovery ranged from 90.1 to 111.5%. No interferences were observed at the retention times of the analytes and IS. This novel LC‐FD method enables the reliable determination of NOR, CIP and LOM in a single chromatographic run, which may be suitable to support human pharmacokinetic‐based studies with those antimicrobial agents. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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