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Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
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Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)00:53

Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)

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Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
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Cycloaddition Reactions: MO Requirements for Thermal Activation01:16

Cycloaddition Reactions: MO Requirements for Thermal Activation

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Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)

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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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Reaction Mechanisms: Rate-limiting Step Approximation01:29

Reaction Mechanisms: Rate-limiting Step Approximation

50
The rate-determining step, or RDS, in a chemical reaction is the slowest step that determines the overall reaction rate. It is identified by using the observed rate law and typically involves approximation methods like the RDS approximation or the steady-state approximation.In the RDS approximation, also known as the rate-limiting-step or equilibrium approximation, the reaction mechanism consists of one or more reversible reactions near equilibrium, followed by a slower RDS, and then one or...
50
Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

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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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Updated: Mar 16, 2026

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
09:37

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry

Published on: October 18, 2019

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Eludir la difusión en reacciones de metátesis en estado sólido controladas cinéticamente

Andrew J Martinolich1, Joshua A Kurzman1, James R Neilson1

  • 1Department of Chemistry, Colorado State University , Fort Collins, Colorado 80523-1872, United States.

Journal of the American Chemical Society
|August 5, 2016
PubMed
Resumen
Este resumen es generado por máquina.

Los investigadores exploraron las reacciones de metástasis en estado sólido para sintetizar materiales inorgánicos. La molienda de reactivos en el aire, en lugar de ambientes sin aire, evita las limitaciones de difusión y las fases intermedias, lo que permite la formación directa de sulfuros metálicos deseados (MS2).

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Área de la Ciencia:

  • Ciencias de los materiales
  • Química del estado sólido
  • Síntesis inorgánica

Sus antecedentes:

  • La difusión en estado sólido a menudo limita la síntesis de nuevos materiales inorgánicos cristalinos.
  • El desarrollo de rutas sintéticas que eludan la difusión es crucial para acceder a compuestos metastables.

Objetivo del estudio:

  • Para investigar las reacciones de metástasis en estado sólido (MCl2 + Na2S2 → MS2 + 2 NaCl) para M = Fe, Co, Ni.
  • Explorar cómo los diferentes métodos de preparación de reactivos influyen en las vías de reacción y en la formación de productos.

Principales métodos:

  • Difracción de rayos X en polvo de sincrotrón in situ.
  • Calorimetría de barrido diferencial.
  • Análisis de la función de distribución de pares.

Principales resultados:

  • Las reacciones sin aire mostraron la formación de productos de difusión limitada con fases intermedias.
  • La molienda de reactivos en el aire condujo a la formación directa de NaCl, desplazando iones en una matriz amorfa.
  • El calentamiento de la mezcla aire-tierra dio lugar a la nucleación directa de MS2, evitando los intermediarios binarios.

Conclusiones:

  • La molienda en el aire altera las vías de reacción mediante la formación de NaCl, que disipa la energía de la celosía y facilita la nucleación directa de MS2.
  • Este método ofrece una ruta para la síntesis a granel de varios compuestos, eludiendo los intermediarios binarios de difusión limitada.