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Catalysis

Catalysis

The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.

Catalysis

Catalysis

Catalysis influences the rate of chemical reactions by providing an alternative reaction pathway with lower activation energy. A catalyst speeds up a reaction, but it is not consumed during the process. The fundamental principle of catalysis is the ability of a catalyst to alter the reaction mechanism, often introducing a more efficient pathway than the uncatalyzed process.In a catalyzed reaction, the catalyst participates directly in the reaction mechanism. It interacts with reactants to form...

Regioselectivity and Stereochemistry of Hydroboration

Regioselectivity and Stereochemistry of Hydroboration

A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.

Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride

Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride

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.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...

Hydroboration-Oxidation of Alkenes

Hydroboration-Oxidation of Alkenes

In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.

Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation

Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation

Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.

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Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction

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El catalizador de oxidación de agua Ru-Hbpp.

Fernando Bozoglian¹, Sophie Romain, Mehmed Z Ertem

¹Institute of Chemical Research of Catalonia (ICIQ), Avinguda Paisos Catalans 16, E-43007 Tarragona, Spain.

Journal of the American Chemical Society

|October 2, 2009

Resumen

Este estudio caracteriza a fondo el catalizador de oxidación de agua Ru-Hbpp, detallando sus estados de oxidación y cinética. Revela la formación de enlaces intramoleculares oxígeno-oxígeno, cruciales para una catálisis eficiente de división del agua.

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Área de la Ciencia:

Química Inorgánica La Química Inorgánica es la química inorgánica.
La catálisis es la catálisis.
La electroquímica es electroquímica.

Sus antecedentes:

Los catalizadores de oxidación del agua son esenciales para la fotosíntesis artificial y la energía renovable.
El complejo Ru-Hbpp es un candidato prometedor para la catálisis de oxidación del agua.
Se necesita una comprensión completa de su mecanismo y estabilidad.

Objetivo del estudio:

Para llevar a cabo una caracterización exhaustiva del catalizador de oxidación de agua Ru-Hbpp.
Para dilucidar las vías mecanicistas de la oxidación del agua, incluyendo la formación de intermedios y la formación de enlaces oxígeno-oxígeno.
Investigar la estabilidad del catalizador y las posibles vías de desactivación bajo condiciones catalíticas.

Principales métodos:

Se emplearon análisis estructurales (rayos X de un solo cristal), espectroscópicos (UV-vis, RMN), cinéticos (flujo detenido) y electroquímicos (voltametría cíclica).
Utilizado el modelado teórico (DFT, CASPT2) para conocimientos mecanicistas.
Realizó experimentos de etiquetado de oxígeno (MS) y mediciones manométricas.

Principales resultados:

Identificó y caracterizó cinco estados de oxidación distintos del complejo Ru-Hbpp, de II,II a IV,IV.
Determinada cinética de transferencia de electrones y parámetros de activación para las etapas de oxidación individuales.
Formación establecida de enlaces intramoleculares oxígeno-oxígeno a través de experimentos de etiquetado de oxígeno y modelado teórico.

Conclusiones:

El catalizador Ru-Hbpp exhibe un comportamiento redox complejo y estados de oxidación bien definidos.
Se ha logrado una comprensión mecánica detallada de la oxidación del agua, incluida la formación de intermedios y el acoplamiento de enlaces O-O.
Se proporcionan información sobre la estabilidad del catalizador y las vías de desactivación para el diseño futuro del catalizador.