Browse
Submit Data
Databases
API
Help

Dataset Information

22 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Redox-ligand sustains controlled generation of CF3 radicals by well-defined copper complex.

ABSTRACT: A well-defined copper complex bearing iminosemiquinone ligands performs single electron reduction of an electrophilic CF3+ source into CF?3 radicals. This redox behavior is enabled by the ligand which shuttles through two different redox states (iminosemiquinone and iminobenzoquinone) while the copper center is preserved as a Cu(ii). This system was used in the trifluoromethylation of silyl enol ethers, heteroaromatics and in the hydrotrifluoromethylation of alkynes. This is the first example of cooperative redox catalysis for the controlled generation of CF?3 radicals.

SUBMITTER: Jacquet J

PROVIDER: S-EPMC5968567 | biostudies-literature | 2016 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Redox-ligand sustains controlled generation of CF3 radicals by well-defined copper complex.

Jacquet Jérémy J Blanchard Sébastien S Derat Etienne E Desage-El Murr Marine M Fensterbank Louis L

Chemical science 20151203 3

A well-defined copper complex bearing iminosemiquinone ligands performs single electron reduction of an electrophilic CF3+ source into CF˙3 radicals. This redox behavior is enabled by the ligand which shuttles through two different redox states (iminosemiquinone and iminobenzoquinone) while the copper center is preserved as a Cu(ii). This system was used in the trifluoromethylation of silyl enol ethers, heteroaromatics and in the hydrotrifluoromethylation of alkynes. This i ...[more]

PMID: 29899928

Similar Datasets

Optimizing Group Transfer Catalysis by Copper Complex with Redox-Active Ligand in an Entatic State.

Project description:Metalloenzymes use earth-abundant non-noble metals to perform high-fidelity transformations in the biological world. To ensure chemical efficiency, metalloenzymes have acquired evolutionary reactivity-enhancing tools. Among these, the entatic state model states that a strongly distorted geometry induced by ligands around a metal center gives rise to an energized structure called entatic state, strongly improving the reactivity. However, the original definition refers both to the transfer of electrons or chemical groups, whereas the chemical application of this concept in synthetic systems has mostly focused on electron transfer, therefore eluding chemical transformations. Here we report that a highly strained redox-active ligand enables a copper complex to perform catalytic nitrogen- and carbon-group transfer in as fast as 2 min, thus exhibiting a strong increase in reactivity compared with its unstrained analogue. This report combines two reactivity-enhancing features from metalloenzymes, entasis and redox cofactors, applied to group-transfer catalysis.

| S-EPMC7083792 | biostudies-literature

Generation and Oxidative Reactivity of a Ni(II) Superoxo Complex via Ligand-Based Redox Non-Innocence.

Project description:Metal ligand cooperativity is a powerful strategy in transition metal chemistry. This type of mechanism for the activation of O2 is best exemplified by heme centers in biological systems. While aerobic oxidations with Fe and Cu are well precedented, Ni-based oxidations are frequently less common due to less-accessible metal-based redox couples. Some Ni enzymes utilize special ligand environments for tuning the Ni(II)/(III) redox couple such as strongly donating thiolates in Ni superoxide dismutase. A recently characterized example of a Ni-containing protein, however, suggests an alternative strategy for mediating redox chemistry with Ni by utilizing ligand-based reducing equivalents to enable oxygen binding. While this mechanism has little synthetic precedent, we show here that Ni complexes of the redox-active ligand tBu,TolDHP (tBu,TolDHP = 2,5-bis((2-t-butylhydrazono)(p-tolyl)methyl)-pyrrole) activate O2 to generate a Ni(II) superoxo complex via ligand-based electron transfer. This superoxo complex is competent for stoichiometric oxidation chemistry with alcohols and hydrocarbons. This work demonstrates that coupling ligand-based redox chemistry with functionally redox-inactive Ni centers enables oxidative transformations more commonly mediated by metals such as Fe and Cu.

| S-EPMC8048103 | biostudies-literature

Synthesis of Well-Defined Gold Nanoparticles Using Pluronic: The Role of Radicals and Surfactants in Nanoparticles Formation.

Project description:Synthesis of gold nanoparticles (GNP) by reacting chloroauric acid (HAuCl4) and Pluronic F127 was thoroughly investigated. The rate of reduction of HAuCl4 and the yield and morphology of GNP strongly depended on the concentration of the reactants and sodium chloride, as well as pH and temperature. Upon completion of the reaction heterogeneous mixtures of small GNP of defined shape and Pluronic aggregates were formed. GNP were separated from the excess of Pluronic by centrifugal filtration. Under optimized conditions the GNP were small (ca. 80 nm), uniform (PDI ~0.09), strongly negatively charged (?-potential -30 mV) and nearly spherical. They were stable in distilled water and phosphate-buffered saline. Purified GNP contained ~13% by weight of an organic component, yet presence of polypropylene oxide was not detected suggesting that Pluronic was not adsorbed on their surface. Analysis of the soluble products suggested that the copolymer undergoes partial degradation accompanied by cleavage of the C-O bonds and appearance of new primary hydroxyl groups. The reaction involves formation of free radicals and hydroperoxides depends on the oxygen concentration. GNP did not form at 4 °C when the micellization of Pluronic was abolished reinforcing the role of the copolymer self-assembly. In conclusion, this work provides insight into the mechanism of HAuCl4 reduction and GNP formation in the presence of Pluronic block copolymers. It is useful for improving the methods of manufacturing uniform and pure GNP that are needed as nanoscale building blocks in nanomedicine applications.

| S-EPMC6835800 | biostudies-literature

Mild, Redox-Neutral Formylation of Aryl Chlorides through the Photocatalytic Generation of Chlorine Radicals.

Project description:We report a redox-neutral formylation of aryl chlorides that proceeds through selective 2-functionalization of 1,3-dioxolane through nickel and photoredox catalysis. This scalable benchtop approach provides a distinct advantage over traditional reductive carbonylation in that no carbon monoxide, pressurized gas, or stoichiometric reductant is employed. The mild conditions give unprecedented scope from abundant and complex aryl chloride starting materials.

| S-EPMC5662441 | biostudies-literature

A novel and well-defined benchmarking method for second generation read mapping.

Project description:BACKGROUND: Second generation sequencing technologies yield DNA sequence data at ultra high-throughput. Common to most biological applications is a mapping of the reads to an almost identical or highly similar reference genome. The assessment of the quality of read mapping results is not straightforward and has not been formalized so far. Hence, it has not been easy to compare different read mapping approaches in a unified way and to determine which program is the best for what task. RESULTS: We present a new benchmark method, called Rabema (Read Alignment BEnchMArk), for read mappers. It consists of a strict definition of the read mapping problem and of tools to evaluate the result of arbitrary read mappers supporting the SAM output format. CONCLUSIONS: We show the usefulness of the benchmark program by performing a comparison of popular read mappers. The tools supporting the benchmark are licensed under the GPL and available from http://www.seqan.de/projects/rabema.html.

| S-EPMC3128034 | biostudies-literature

Voltammetric Detection of Glucose-The Electrochemical Behavior of the Copper Oxide Materials with Well-Defined Facets.

Project description:Cu2O nanomaterials with well-defined facets and uniform size were synthesized by a wet-chemical method. Regardless of the additive composition, powders crystallize mostly in cuprite form. To compare their electrochemical behavior, the obtained materials were deposited on carbon glassy electrodes. The response to glucose from the materials with different exposed facets was recorded with a delay at the anodic curve. The chronoamperometric analyses (AMP) exhibited a lower signal in contrast to the cyclic voltammetry data (CV), indicating that the number of active sites involved in glucose oxidation processes resulting from the structure of the material is insufficient. For samples with dominant (100) or (111) planes, a typical characteristic was observed, however, with an additional peak at the anodic curve. The location of the peaks is approximately the same and no significant differences from the AMP and CV analysis were observed. The sample enclosed by the (111) facets exhibited higher activity; however, as a result of the redox reaction with glucose molecules, the surface state is changing. Cu2O materials enclosed by (100) planes exhibited optimal sensitivity as well as a large detective range. Samples with differential facet exposition present various current-potential profiles, as the effect of binder-particle interaction with Nafion.

| S-EPMC9269370 | biostudies-literature

A Copper(I) Complex with Two Unpaired Electrons, Synthesised by Oxidation of a Copper(II) Complex with Two Redox-Active Ligands.

Project description:Two homoleptic copper(II) complexes [Cu(L1)2 ] and [Cu(L2)2 ] with anionic redox-active ligands were synthesised, one with urea azine (L1) and the other with thio-urea azine (L2) ligands. One-electron oxidation of the complexes initiates an unprecedented redox-induced electron transfer process, leading to monocationic copper(I) complexes [Cu(L1)2 ]+ and [Cu(L2)2 ]+ with two oxidised ligands. While [Cu(L1)2 ]+ is best described as a CuI complex with two neutral radical ligands that couple antiferromagnetically, [Cu(L2)2 ]+ is a CuI complex with two clearly different ligand units in the solid state and with a magnetic susceptibility close to a diamagnetic compound. Further one-electron oxidation of the complex with L1 ligands results in a dication [Cu(L1)2 ]2+ , best described as a CuI complex with a twofold oxidised, monocationic ligand and a neutral radical ligand. The stability in at least three redox states, the accumulation of spin density at the ligands and the facile ligand-metal electron transfer make these complexes highly attractive for a variety of applications; here the catalytic aerobic oxidation of alcohols to aldehydes is tested.

| S-EPMC8596453 | biostudies-literature

Well-Defined Chiral Gold(III) Complex Catalyzed Direct Enantioconvergent Kinetic Resolution of 1,5-Enynes.

Project description:The development of a gold(III) catalyzed direct enantioconvergent 1,5-enyne cycloisomerization and kinetic resolution reaction is described. The transformation results in highly enantioenriched bicyclo[3.1.0]hexenes at all levels of conversion, with no racemization or symmetrization taking place during the course of the reaction, and simultaneously affords optically enriched 1,5-enynes. This report marks the first highly enantioselective transformation catalyzed by a well-defined cationic gold(III) catalyst and demonstrates the unique potential of gold(III) complexes in enantioselective catalysis.

| S-EPMC5911161 | biostudies-literature

Bis(2,2'-bipyridil)Copper(II) Chloride Complex: Tyrosinase Biomimetic Catalyst or Redox Mediator?

Project description:In this article, construction of amperometric sensor(s) based on screen-printed carbon electrodes covered by thin layers of two types of carbon nanomaterials serving as amplifiers, and containing [Cu(bipy)2Cl]Cl∙5H2O complex is reported. Their performance and biomimetic activity towards two selected neurotransmitters (dopamine and serotonin) was studied mainly using flow injection analysis (FIA). The important parameters of FIA such as working potential, flow rate, and pH were optimized. The mechanism of the catalytic activity is explained and experimentally confirmed. It reveals that presence of hydrogen peroxide plays a crucial role which leads to answer the title question: can presented complex really be considered as a tyrosinase biomimetic catalyst or only as a redox mediator?

| S-EPMC7795177 | biostudies-literature

Size-dependent redox behavior of iron observed by in-situ single nanoparticle spectro-microscopy on well-defined model systems.

Project description:Understanding the chemistry of nanoparticles is crucial in many applications. Their synthesis in a controlled manner and their characterization at the single particle level is essential to gain deeper insight into chemical mechanisms. In this work, single nanoparticle spectro-microscopy with top-down nanofabrication is demonstrated to study individual iron nanoparticles of nine different lateral dimensions from 80?nm down to 6?nm. The particles are probed simultaneously, under same conditions, during in-situ redox reaction using X-ray photoemission electron microscopy elucidating the size effect during the early stage of oxidation, yielding time-dependent evolution of iron oxides and the mechanism for the inter-conversion of oxides in nanoparticles. Fabrication of well-defined system followed by visualization and investigation of singled-out particles eliminates the ambiguities emerging from dispersed nanoparticles and reveals a significant increase in the initial rate of oxidation with decreasing size, but the reactivity per active site basis and the intrinsic chemical properties in the particles remain the same in the scale of interest. This advance of nanopatterning together with spatially-resolved single nanoparticle X-ray absorption spectroscopy will guide future discourse in understanding the impact of confinement of metal nanoparticles and pave way to solve fundamental questions in material science, chemical physics, magnetism, nanomedicine and nanocatalysis.

| S-EPMC4702129 | biostudies-literature