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Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction01:22

Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction

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The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
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Radical Reactivity: Concentration Effects01:20

Radical Reactivity: Concentration Effects

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In a radical reaction, the concentration of starting materials governs the selectivity of a radical. For example, the reaction between an alkyl halide and an alkene, in the presence of tin hydride and AIBN, begins with the generation of a tin radical. The generated radical then abstracts halogen from the alkyl halide, producing an alkyl radical. This alkyl radical can either react with tin hydride, yielding an alkane, or add to an alkene, generating a nitrile-stabilized radical, eventually...
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Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

3.1K
Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
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Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

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The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
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Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

2.1K
Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
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Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride01:26

Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride

2.2K
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
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Applying Dynamic Strain on Thin Oxide Films Immobilized on a Pseudoelastic Nickel-Titanium Alloy
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Inducción de la reactividad por tensión de grupo en estructuras de titanio

Eloy P Gómez-Oliveira1, Vitor Fernandes de Almeida2, Javier Castells-Gil3

  • 1Functional Inorganic Materials Team, Instituto de Ciencia Molecular (ICMol), Universitat de València, 46980 València, Spain.

Journal of the American Chemical Society
|December 24, 2025
PubMed
Resumen
Este resumen es generado por máquina.

Demostramos la ingeniería de tensión de grupo en estructuras orgánicas de titanio mediante la sustitución de cationes. Este método distorsiona previsiblemente los grupos de metal-oxo, mejorando la actividad redox para aplicaciones como la metanación fotocatalítica de CO2.

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Área de la Ciencia:

  • Ciencias de los materiales
  • Química
  • Catálisis

Sus antecedentes:

  • Las estrategias para distorsionar los grupos de metal-oxo en las estructuras moleculares son limitadas.
  • El control de la separación de cargas y la actividad redox en los marcos es crucial.

Objetivo del estudio:

  • Presentar una prueba de concepto para la ingeniería de deformación de clúster en marcos orgánicos de titanio.
  • Investigar el efecto de la sustitución catiónica en las propiedades de distorsión y redox del racimo.

Principales métodos:

  • Utilizado MUV-10 (un marco orgánico de titanio) como un sistema modelo.
  • Ca2+ sustituido por cationes de tierra alcalina más grandes (Sr2+, Ba2+) para inducir la tensión.
  • Cambios estructurales analizados y actividad fotocatalítica (metanación de CO2).

Principales resultados:

  • Se lograron distorsiones predecibles de los grupos Ti2M2 y una transformación de células cúbicas a tetragonales.
  • Se observó una geometría de coordinación Ti-O alterada y una transferencia de carga mejorada de ligando a metal.
  • Fotogeneración promovida de los sitios de Ti3+, validada por la metanación fotocatalítica con CO2.

Conclusiones:

  • Ingeniería de deformación en racimo establecida como método para modular la reactividad redox en sólidos moleculares.
  • Catálisis de óxido vinculado y química reticular a través de la cepa de racimo.
  • Repuso el factor de tolerancia de Goldschmidt para racionalizar la tensión en los marcos reticulares.