Video Experimental Relacionado

Updated: May 18, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphos^Ph Complexes

Published on: April 10, 2015

Hidricidad termodinámica y cinética de los complejos de hidruro de rutenio (II)

Yasuo Matsubara¹, Etsuko Fujita, Mark D Doherty

¹Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973-5000, United States.

Journal of the American Chemical Society

|September 13, 2012

Resumen

Este estudio cuantifica la hidricidad de los complejos de hidruro de rutenio en el acetonitrilo, revelando un rango comprimido en comparación con el agua. Estos hallazgos son cruciales para las aplicaciones de catálisis y almacenamiento de energía solar.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
La electroquímica es electroquímica.
La fotoquímica es la fotoquímica.

Sus antecedentes:

La hidricidad de los hidruros de metales de transición es vital para la catálisis y el almacenamiento de energía solar.
Los datos de hidricidad existentes son limitados, especialmente para los disolventes acuosos, lo que dificulta las comparaciones.
Los complejos de hidruro de rutenio ofrecen un sistema modelo para estudiar los efectos del disolvente en la hidricidad.

Objetivo del estudio:

Para determinar los valores de hidricidad de los complejos de hidruro de rutenio en el acetonitrilo.
Para comparar estos valores con los reportados previamente en agua.
Para entender la influencia del disolvente en el rango de hidricidad de estos complejos.

Principales métodos:

Ciclo termodinámico que incluye mediciones de acidez y potenciales electroquímicos para [Ru(η(6) -C6Me6) ((bpy) H]++.
Reacciones de transferencia de hidruro con aceptores orgánicos y espectroscopia de RMN 1H para [Ru(tpy) ((bpy) H]+.
Espectroscopia UVvis y cálculos de estructura electrónica DFT para caracterizar complejos.

Principales resultados:

Hidricidades estimadas en el acetonitrilo: 54 ± 2 kcal/mol para [Ru((η(6) -C6Me6) ((bpy) H]+ y 39 ± 3 kcal/mol para [Ru(tpy) ((bpy) H]+ .
Los valores correspondientes en el agua fueron de 31 y 22 kcal/mol, respectivamente.
Los valores estimados de pKa en el acetonitrilo fueron de 22,5 ± 0,1 para [Ru(η(6) -C6Me6) ((bpy) H]+ y de 32 ± 3 para [Ru(tpy) ((bpy) H]+ .

Conclusiones:

La transferencia de disolvente del acetonitrilo al agua comprime el rango de hidricidad de los complejos de hidruro de rutenio.
Se identificaron complejos de rutenio con ligandos bpy y tpy reducidos.
El estudio proporciona datos comparativos esenciales para la hidricidad en diferentes disolventes.

Más Videos Relacionados

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Published on: July 27, 2022

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

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

Published on: August 23, 2018

Videos de Conceptos Relacionados

Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration

Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration

The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.

Aldehydes and Ketones with Water: Hydrate Formation

Aldehydes and Ketones with Water: Hydrate Formation

An oxygen-based nucleophile, like water, can undergo addition reactions with aldehydes and ketones. The reaction leads to the formation of hydrates, also referred to as 1,1-diols or geminal diols.
The formation of hydrates is a reversible reaction. Hydrate formation is influenced by steric and electronic factors accompanying the alkyl substituents on the carbonyl group: The rate of hydrate formation increases with a decrease in the number of alkyl groups attached to the carbonyl carbon. Hence,...

Electrophilic Addition of HX to 1,3-Butadiene: Thermodynamic vs Kinetic Control

Electrophilic Addition of HX to 1,3-Butadiene: Thermodynamic vs Kinetic Control

The addition of a hydrogen halide to 1,3-butadiene gives a mixture of 1,2- and 1,4-adducts. Since more substituted alkenes are more stable, the 1,4-adduct is expected to be the major product. However, the product distribution is strongly influenced by temperature; low temperature favors the 1,2-adduct, whereas the 1,4-adduct is predominant at high temperature.

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,...

Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration

Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration

Introduction
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.

Acid-Catalyzed Hydration of Alkenes

Acid-Catalyzed Hydration of Alkenes

Alkenes react with water in the presence of an acid to form an alcohol. In the absence of acid, hydration of alkenes does not occur at a significant rate, and the acid is not consumed in the reaction. Therefore, alkene hydration is an acid-catalyzed reaction.