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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

Fácil activación heterolítica de Ru-H2 y transferencia intramolecular de protones asistida por centros N básicos en

Félix A Jalón¹, Blanca R Manzano, Agustín Caballero

¹Departamento de Química Inorgánica, Orgánica y Bioquímica, IRICA, Departamento de Química Física, Universidad de Castilla-La Mancha, Avda. C. J. Cela 10, 13071 Ciudad Real, Spain. Felix.Jalon@uclm.es

Journal of the American Chemical Society

|November 3, 2005

Resumen

El ligando de la fosfina PPh2py en los complejos [Cp*RuH(P)2] facilita la transferencia reversible de protones y la liberación de H2. Este comportamiento permite el etiquetado catalítico de deuterio, mostrando una fácil activación heterolítica de H2.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
La catálisis de la catálisis.
Química computacional es la química computacional.

Sus antecedentes:

El entorno del ligando en los complejos organometálicos influye significativamente en la reactividad.
Los ligandos de fosfina como la trifenilfosfina (PPh3) son comunes en la química del rutenio.
Comprender los mecanismos de transferencia de protones es crucial para las aplicaciones catalíticas.

Objetivo del estudio:

Para investigar el efecto del ligando de la fosfina PPh2py en las reacciones de transferencia de protones en los complejos [Cp*RuH(P) 2].
Para explorar la actividad catalítica de estos complejos en el etiquetado de deuterio.
Para aclarar el mecanismo de la transferencia de protones y la liberación de hidrógeno utilizando métodos computacionales.

Principales métodos:

Síntesis y caracterización de complejos de rutenio con ligandos PPh2py.
Reacciones de protonación con ácido tetrafluorobórico (HBF4) a bajas temperaturas.
Experimentos de etiquetado de deuterio utilizando el metanol-d4.
Teoría funcional de la densidad (DFT/B3LYP) cálculos de coordenadas de reacción.

Principales resultados:

El ligando PPh2py altera el control cinético, lo que lleva a complejos dihidruro o dihidrógeno-enlazados después de la protonación.
Estos complejos exhiben una fácil transferencia intramolecular de protones y una liberación reversible de H2 a temperatura ambiente.
Los complejos de rutenio son catalizadores activos para el etiquetado de deuterio de H2, lo que demuestra la activación reversible de H2.

Conclusiones:

El ligando PPh2py juega un papel crítico para permitir la transferencia reversible de protones y las vías de activación / liberación de H2.
La actividad catalítica observada en el etiquetado de deuterio pone de relieve la utilidad práctica de estos complejos.
Los estudios computacionales confirman una vía de baja energía para la interconversión entre dihidruro clásico y especies de dihidrógeno no clásicas.

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