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41.
Latronico M Polini F Gallo V Mastrorilli P Calmuschi-Cula B Englert U Re N Repo T Räisänen M 《Inorganic chemistry》2008,47(21):9779-9796
The protonation of the dinuclear phosphinito bridged complex [(PHCy2)Pt(mu-PCy2){kappa(2)P,O-mu-P(O)Cy2}Pt(PHCy2)] (Pt-Pt) (1) by Br?nsted acids affords hydrido bridged Pt-Pt species the structure of which depends on the nature and on the amount of the acid used. The addition of 1 equiv of HX (X = Cl, Br, I) gives products of formal protonation of the Pt-Pt bond of formula syn-[(PHCy2)(X)Pt(mu-PCy2)(mu-H)Pt(PHCy2){kappaP-P(O)Cy2}] (Pt-Pt) (5, X = Cl; 6, X = Br; 8, X = I), containing a Pt-X bond and a dangling kappa P-P(O)Cy2 ligand. Uptake of a second equivalent of HX results in the protonation of the P(O)Cy2 ligand with formation of the complexes [(PHCy2)(X)Pt(mu-PCy2)(mu-H)Pt(PHCy2){kappaP-P(OH)Cy2}]X (Pt-Pt) (3, X = Cl; 4, X = Br; 9, X = I). Each step of protonation is reversible, thus reactions of 3, 4, with NaOH give, first, the corresponding neutral complexes 5, 6, and then the parent compound 1. While the complexes 3 and 4 are indefinitely stable, the iodine analogue 9 transforms into anti-[(PHCy2)(I)Pt(mu-PCy2)(mu-H)Pt(PHCy2)(I)] (Pt-Pt) (7) deriving from substitution of an iodo group for the P(OH)Cy2 ligand. Complexes 3 and 4 are isomorphous crystallizing in the triclinic space group P1 and show an intramolecular hydrogen bond and an interaction between the halide counteranion and the POH hydrogen. The occurrence of such an interaction also in solution was ascertained for 3 by (35)Cl NMR. Multinuclear NMR spectroscopy (including (31)P-(1)H HOESY) and density-functional theory calculations indicate that the mechanism of the reaction starts with a prior protonation of the oxygen with formation of an intermediate (12) endowed with a six membered Pt(1)-X...H-O-P-Pt(2) ring that evolves into thermodynamically stable products featuring the hydride ligand bridging the Pt atoms. Energy profiles calculated for the various steps of the reaction between 1 and HCl showed very low barriers for the proton transfer and the subsequent rearrangement to 12, while a barrier of 29 kcal mol(-1) was found for the transformation of 12 into 5. 相似文献
42.
Dr. Linda Iffland-Mühlhaus Dr. Beatrice Battistella Dr. Daniel Siegmund Prof. Dr. Kallol Ray Prof. Dr. Ulf-Peter Apfel 《欧洲无机化学杂志》2023,26(30):e202300418
Cobalt complexes are extensively studied as bioinspired models for non-heme oxygenases as they facilitate both the stabilization and characterization of metal-oxygen intermediates. As an analog to the well-known Co(cyclam) complex Co{N4} (cyclam=1,4,8,11-tetraazacyclotetradecane), the CoII complex Co{i-N4} with the isomeric isocyclam ligand (isocyclam=1,4,7,11-tetraazacyclotetradecane) was synthesized and characterized. Despite the identical N4 donor set of both complexes, Co{i-N4} enables the 2e−/2H+ reduction of O2 with a lower overpotential (ηeff of 385 mV vs. 540 mV for Co{N4} ), albeit with a diminished turnover frequency. Characterization of the intermediates formed upon O2 activation of Co{i-N4} reveals a structurally identified stable μ-peroxo CoIII dimer as the main product. A superoxo CoIII species is also formed as a minor product, as indicated by EPR spectroscopy. In further reactivity studies, the electrophilicity of these in situ generated Co−O2 species was demonstrated by the oxidation of the O−H bond of TEMPO−H (2,2,6,6-tetramethylpiperidin-1-ol) via a H atom abstraction process. Unlike the known Co(cyclam), Co{i-N4} can be employed in oxygen atom transfer reactions oxidizing triphenylphosphine to the corresponding phosphine oxide highlighting the impact of geometrical modifications of the ligand while preserving the ring size and donor atom set on the reactivity of biomimetic oxygen activating complexes. 相似文献
43.
Jacopo Sgrignani Filomena De Luca Hayarpi Torosyan Jean-Denis Docquier Da Duan Beatrice Novati Fabio Prati Giorgio Colombo Giovanni Grazioso 《Journal of computer-aided molecular design》2016,30(10):851-861
β-Lactamases are bacterial enzymes conferring resistance to β-lactam antibiotics in clinically-relevant pathogens, and represent relevant drug targets. Recently, the identification of new boronic acids (i.e. RPX7009) paved the way to the clinical application of these molecules as potential drugs. Here, we screened in silico a library of ~1400 boronic acids as potential AmpC β-lactamase inhibitors. Six of the most promising candidates were evaluated in biochemical assays leading to the identification of potent inhibitors of clinically-relevant β-lactamases like AmpC, KPC-2 and CTX-M-15. One of the selected compounds showed nanomolar K i value with the clinically-relevant KPC-2 carbapenemase, while another one exhibited broad spectrum inhibition, being also active on Enterobacter AmpC and the OXA-48 class D carbapenemase. 相似文献
44.
Rafael Schiwon Beatrice Braun Ramona Metzinger Christian Limberg 《无机化学与普通化学杂志》2016,642(21):1198-1206
While addition of [Cp2ReH] to [Bi(OtBu)3] leads to an equilibrium containing [Cp2Re‐Bi(OtBu)2], [{Cp2Re}2Bi(OtBu)], tBuOH and [CpRe(μ‐η5,η1‐C5H4)Bi–ReCp2], in the presence of water [{(Cp2Re)2Bi}2O] ( 1 ) is formed selectively. Also [FpH] [Fp = (η5‐C5H5)(CO)2Fe] can be employed as a precursor to form heterometallic bismuth compounds. Synthesis of [FpBi{OCH(CF3)2}2]2 ( 5 ) can be achieved by reaction of [FpH] with [Bi{OCH(CF3)2}3(thf)]2 and carboxylates [FpBi(O2CR)2]2 are generated upon treatment of [FpH] with [Bi(O2CR)3] (R = CH3, tBu). While the compounds [Fp‐Bi(O2CR)2]2 can also be obtained from reactions with Fp‐Fp, they are formed far more readily using [FpH] as the precursor. They typically crystallize as dimers, like the alkoxide 5 . A monomeric compound of the type [Fp‐BiX2] ( 6 ) could be isolated for X = thd (tetramethylheptanedionate), that is, after the reaction of [FpH] with [Bi(thd)3]. Altogether, the results demonstrate the potential of [FpH] as a precursor for [Fp‐BiX2] compounds, which are formed in reactions with bismuth alkoxides, carboxylates and diketonates. 相似文献
45.
Trapping Aluminum Hydroxide Clusters with Trisilanols during Speciation in Aluminum(III)–Water Systems: Reproducible,Large Scale Access to Molecular Aluminate Models 下载免费PDF全文
Dr. Kapil Shyam Lokare Nicolas Frank Dr. Beatrice Braun‐Cula Dr. Itziar Goikoetxea Prof. Dr. Joachim Sauer Prof. Dr. Christian Limberg 《Angewandte Chemie (International ed. in English)》2016,55(40):12325-12329
To gain molecular level insights into the properties of certain functions and units of extended oxides/hydroxides, suitable molecular model compounds are needed. As an attractive route to access such compounds the trapping of early intermediates during the hydrolysis of suitable precursor compounds with the aid of stabilizing ligands is conceivable, which was tested for the aluminum(III)/water system. Indeed, trisilanols proved suitable trapping reagents: their presence during the hydrolysis of AliBu2H in dependence on the amount of water used allowed for the isolation of tri‐ and octanuclear aluminum hydroxide cluster complexes [Al3(μ2‐OH)3(THF)3(PhSi(OSiPh2O)3)2] ( 1 ) and [Al8(μ3‐OH)2(μ2‐OH)10(THF)3(p‐anisylSi(OSiPh2O)3)4] ( 2 ). 1 can be regarded as the Al(OH)3 cyclic trimer, where six protons have been replaced by silyl residues. While 2 features a unique [Al8(μ3‐OH)2(μ2‐OH)10]12+ core. In contrast to most other known aggregates of this type, 1 and 2 can be readily prepared at reasonable scales, dissolve in common solvents, and retain an intact framework even in the presence of excessive amounts of water. This finding paves the way to future research addressing the reactivity of the individual functional groups. 相似文献
46.
Goodrich CP Kirmizialtin S Huyghues-Despointes BM Zhu A Scholtz JM Makarov DE Movileanu L 《The journal of physical chemistry. B》2007,111(13):3332-3335
We used single-channel electrical recordings and Langevin molecular dynamics simulations to explore the electrophoretic translocation of various beta-hairpin peptides across the staphylococcal alpha-hemolysin (alphaHL) protein pore at single-molecule resolution. The beta-hairpin peptides, which varied in their folding properties, corresponded to the C terminal residues of the B1 domain of protein G. The translocation time was strongly dependent on the electric force and was correlated with the folding features of the beta-hairpin peptides. Highly unfolded peptides entered the pore in an extended conformation, resulting in fast single-file translocation events. In contrast, the translocation of the folded beta-hairpin peptides occurred more slowly. In this case, the beta-hairpin peptides traversed the alphaHL pore in a misfolded or fully folded conformation. This study demonstrates that the interaction between a polypeptide and a beta-barrel protein pore is dependent on the folding features of the polypeptide. 相似文献
47.
48.
Mohand Ouidir BOUSSOUM Abdelkader ALI-NEHARI Rachida OULDMOKHTAR Beatrice GEORGE 《Turkish Journal of Chemistry》2021,45(5):1576
The aim of our work is to study the dyeing properties of extracts from natural sources such as Papaver rhoeas by modifying the conditions of the dyeing process, choosing other substrates that could be pretreated by innovative and environmentally friendly processes. The results obtained show a fairly high fixation of the extracts on the natural and artificial fibers. The use of mordants allowed the dye to be better fixed on the dyed fibers and to give several shades to the fabric. The rate of essential oil contained in Papaver rhoeas was considered important by the Clevenger process. Screening of extractive revealed the presence of polyphenols, saponins, sterols, alkaloids and flavonoids. In this study, the extractive from Papaver rhoeas was investigated as textile dyestuff. 相似文献
49.
Eric J. Goethals Wouter Reyntjens Xiaochun Zhang Beatrice Verdonck Ton Loontjens 《Macromolecular Symposia》2000,157(1):93-100
Sequential living cationic polymerization of octadecyl vinyl ether (ODVE) and methyl vinyl ether (MVE) was used for the preparation of amphiphilic ABA‐type block copolymers. The polymerization of ODVE was initiated with the trimethyl silyl iodide/1,1,3,3‐tetramethoxy propane/ZnI2 system at 0°C in toluene. The living bifunctional polyODVE thus obtained was used as initiator for the polymerization of MVE. Below the LCST of polyMVE (37°C), the copolymers are amphiphiles. Above the LCST of polyMVE, the polyMVE‐blocks become hydrophobic and the amphiphilic nature of the block copolymer is lost. This was demonstrated by using the block copolymers as emulsifiers for water/decane mixtures. The emulsions were stable for several hours at room temperature, while the emulsion stability decreased to about 30 seconds at 40°C. PolyMVE‐α,ω‐bis‐methacrylates were obtained by end‐capping of living bifunctional polyMVE with 2‐hydroxyethyl methacrylate (HEMA). Copolymerization of these bis‐macromers with HEMA leads to segmented networks. The networks showed a reversible swelling/deswelling behavior in water as a function of temperature. This is caused by a change of the hydrophilicity of the polyMVE segments in the networks. Hexa(chloromethyl)melamine, combined with zinc chloride was found to be an efficient hexafunctional initiator for the living cationic polymerization of vinyl ethers. This simple initiating system opens new ways for the synthesis of endgroup‐functionalized star‐shaped poly(vinyl ethers). 相似文献
50.
Beatrice Malgesini Eduard Felder Nicola Mongelli Gianluca Papeo 《Molecular diversity》2009,13(1):53-56
Polyfluorinated N-α-Fmoc--Boc-l-lysine represents the best-in-class among a set of polyfluorinated amino acids (PFAs) which are useful tools for 19F NMR-Based Screening. In this communication, optimized reaction conditions that allowed for the multi-gram preparation of
this unnatural amino acid are reported. 相似文献