Search results for "Oxime"
showing 10 items of 148 documents
Desarrollo de Nanocompuestos de Celulosa Bacteriana para Aplicaciones Biomédicas
2014
La celulosa bacteriana es un polisacárido obtenido a partir de microorganismos de la especie Gluconacetobacter cuando son cultivados en medios que contienen fuentes de carbono y nitrógeno. El material que se obtiene a partir de los procesos bioquímicos que ocurren dentro de la membrana celular de las bacterias se presenta físicamente como un gel que contiene agua y fibras de celulosa de alta pureza, cuyas dimensiones de sección se encuentran en el orden de los nanómetros. Debido a sus buenas propiedades, las aplicaciones de los materiales basados en celulosa bacteriana se incluyen en la industria del papel, alimentaria, farmacéutica y en biomedicina. La mayoría de investigaciones para la fa…
New Route to Polynuclear Ni(II) and Cu(II) Complexes with Bridging Oxime Groups That Are Inaccessible by Conventional Preparations
2019
A series of new polynuclear complexes of divalent Ni and Cu with 2-cyano-2-oximino-acetic acid (later AACO2-) were obtained as the result of the ligand modification reaction in the process of complexation, using 2-cyano-2-oximino-acetates such as methyl- (later as MeCO), and ethyl- (as ECO later on). Synthesized compounds were characterized by spectroscopic methods, thermal analysis, magnetochemistry, and X-ray crystallography. Crystal data revealed the formation of the dimeric [Ni(AACO)(H2O)3]2·H2O (1), trimeric K2[Ni3(AACO)4(H2O)4]·4H2O (2), and K2[Cu3(AACO)4(H2O)4]·4H2O (3) complexes, with bridging NO-groups cyanoxime dianions. In the latter two compounds, the AACO2– anions adopt cis-arr…
Theoretical studies on cycloaddition reactions
2014
Cycloaddition reactions represent one of the most powerful processes in organic chemistry. The most common types of cycloaddition reactions are the Diels-Alder (DA) and the 1,3-dipolar cycloaddition reactions (1,3-DCs) which lead to five and six membered rings, respectively. In our ongoing efforts to contribute to the understanding of DA and 1,3-DCs; we studied the following using the B3LYP/6-31G(d) level of theory: 1. The 1,3-DCs of the pyridinium-3-olates and pyrazinium-3-olates with methyl acrylate and methyl methacrylate [1,2]. 2. The competitive hetero-DA and 1,3-DCs of methyl glyoxylate oxime and its tautomeric nitrone with cyclopentadiene in the absence and in the presence of BF3 as …
Understanding the formation of [3+2] and [2+4] cycloadducts in the Lewis acid catalysed reaction between methyl glyoxylate oxime and cyclopentadiene:…
2013
The formation of the formal [3+2] and [2+4] cycloadducts in the Lewis acid (LA) catalysed reaction of cyclopentadiene (Cp, 1) with methyl glyoxylate oxime (MGO, 2a) has been theoretically studied using DFT methods. Coordination of BF3 LA to the oxygen atom of MGO 2a not only increases the electrophilicity of the oxime, but also makes the corresponding tautomeric BF3:nitrone complex 8b the reactive species. The reaction is characterised by the nucleophilic attack of Cp 1 on the carbon atom of the corresponding BF3:nitrone complex 8b. The subsequent ring closure at the end of the reaction allows the formation of the [3+2] or [2+4] cycloadducts. ELF bonding analysis of selected points on the i…
Thioester-functionalised and oxime-based hexametallic manganese(iii) single-molecule magnets
2017
Two novel hexametallic MnIII complexes of formulae [Mn6(μ3-O)2(H2N-sao)6(3-atpa)2(EtOH)6]·2EtOH·2H2O (1) and [Mn6(μ3-O)2(H2N-sao)6(6-atha)2(EtOH)6]·6EtOH (2) [H2N-saoH2 = salicylamidoxime, 3-hatpa = 3-(acetylthio)propionic acid, 6-hatha = 6-(acetylthio)hexanoic acid] have been synthesised by using thioester-carboxylate ligands and magnetostructurally characterised. 1 crystallises in the triclinic system with space group P and 2 crystallises in the monoclinic system with space group P21/c. The study of the dc and ac magnetic susceptibility reveals single-molecule magnet behaviour for both compounds with spin-ground states S = 12 and S = 4 for 1 and 2, respectively. Hence, 1 and 2 are new mem…
Triple associates based on (oxime)Pt(II) species, 18-crown-6, and water: Synthesis, structural characterization, and DFT study
2014
Abstract The associates 2(cis-[PtCl2(acetoxime)2])⋅18-crown-6⋅2H2O (1), 2(cis-[PtBr2(acetoxime)2])⋅18-crown-6⋅2H2O (2), and trans-[PtCl2(acetaldoxime)2]⋅(18-crown-6)⋅2H2O (3) were synthesized by co-crystallization of free corresponding platinum species and 18-crown-6 from wet solvents and characterized by 1H NMR and IR spectroscopies, high-resolution mass-spectrometry (ESI), TG/DTA, and X-ray crystallography. The (oxime)Pt(II) species are assembled with 18-crown-6 and water by hydrogen bonding between the hydroxylic hydrogen atoms of the oxime ligands and the oxygen atom of water and between the hydrogen atoms of water and the oxygen atoms of 18-crown-6. In 2(cis-[PtX2(acetoxime)2])⋅18-crow…
Structural and magnetic properties of polynuclear oximate copper complexes with different topologies
2017
Abstract Two new copper(II) complexes containing the methyl(2-pyridyl)ketone oxime ligand (mpkoH) [Cu3(OH)(ClO4)2(mpko)3]·CH3OH (1) and [Cu(ClO4)(mpko)(mpkoH)]n (2) have been prepared from Cu(ClO4)2 and mpkoH in different metal-to-ligand molar ratios. In addition, the compound [Cu{(mpko)2BF2}(H2O)](BF4) (3) [(mpko)2BF2 is the fluoroboration product of the oxime] has been obtained when replacing Cu(ClO4)2 by Cu(BF4)2. Compound 1 is an isolated triangle with a {Cu3(µ3-OH)}5+ core, whereas 2 is a chain of CuII ions linked by anionic mpko− bridges. 1 exhibits strong antiferromagnetic competing interactions, as well as antisymmetric exchange. On the other hand, very weak ferromagnetic interactio…
Exchange coupling in a thiocyanato-bridged copper(II) chain: Computational approach to magnetostructural correlations
2021
Abstract In this article we report the synthesis and magneto-structural characterization of two new copper(II) compounds with thiocyanato and methyl(2-pyridil) ketone oxime (mpkOH), namely [Cu(NCS)(mpkO)(mpkOH)] (1) and [Cu(µ-NCS)(NCS)(mpkOH)]n (2). Compound 1 is a mononuclear complex that crystallizes as discrete units. Conversely, compound 2 is a single equatorial-axial end-to-end thiocyanato bridged polymeric chain of Cu(II) with the oxime as a co-ligand. The coordination geometry around the Cu(II) centers is distorted square pyramidal for 1 and 2. The magnetic susceptibility data for 2 reveal weak intrachain antiferromagnetic coupling, with J value −0.74(3) cm−1 and g = 2.10(1). The ap…
Are Heme-Dependent Enzymes Always Using a Redox Mechanism? A Theoretical Study of the Kemp Elimination Catalyzed by a Promiscuous Aldoxime Dehydratase
2020
The design of biocatalysts is a goal to improve the rate, selectivity and environmental friendship of chemical processes in biotechnology. In this regard, the use of computational techniques has provided valuable assistance in the design of enzymes with remarkable catalytic activity. In this paper, hybrid QM/MM simulations have allowed getting an insight into the mechanism of a promiscuous aldoxime dehydratase (OxdA) for the Kemp elimination. We first demonstrate that, based on the use of linear response approximation (LRA) methods, the lowest energy electronic state of the benzisoxazole placed in the active sit of OxdA corresponds to a singlet state, being the triplet and the quintet state…
A novel Cu(II) dimer containing oxime-hydrazone Schiff base ligands with an unusual mode of coordination: Study of magnetic, autoreduction and soluti…
2013
Abstract Synthesis of a new hydrazone based Schiff base ligand, 3-methylpyrazole-5-carbohydrazone of 2,3-butanedione monoxime (HL) is reported. The reaction of Cu(ClO4)2·6H2O with HL in any ratio in ethanol affords the dinuclear complex [CuL(EtOH)]2(ClO4)2·2H2O (1). An unusual coordination mode of the ligand was observed, in which the ligand forms stable six and five membered chelate rings around the metal centres without enolization of the carbonyl group of the hydrazone moiety. The same coordination behavior of the ligand was observed in its cobalt(III) complex. The reaction of CoCl2·6H2O in methanol with the ligand HL affords the mononuclear complex [CoL2]Cl (2). Both 1 and 2 were charac…