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Los escurridizos complejos de 16 electrones Cp*M(NO)Me(2)(M = Mo, W) y sus conversiones espontáneas a isómeros
W B Sharp1, P J Daff, W S McNeil
1Contribution from the Department of Chemistry, The University of British Columbia, Vancouver, British Columbia, Canada V6T 1Z1.
Journal of the American Chemical Society
|June 28, 2001
Resumen
Este estudio detalla la síntesis y la reactividad de un nuevo complejo dimetilo, Cp*Mo(NO)Me(2). El complejo exhibe isomerización y electrofilicidad únicas, ofreciendo información sobre la química organometálica.
Área de la Ciencia:
- Química organometálica Química orgánica de los metales.
- Química del molibdeno Química del molibdeno
- Coordinación Química de la Coordinación
Sus antecedentes:
- La síntesis de complejos organometálicos con arreglos específicos de ligandos es crucial para comprender la reactividad.
- Los complejos de nitrosilo de molibdeno son de interés debido a sus diversas propiedades electrónicas y potenciales aplicaciones catalíticas.
Objetivo del estudio:
- Para sintetizar y caracterizar un nuevo complejo de dimetilo molibdeno nitrosilo, Cp*Mo(NO)Me(2).
- Investigar la reactividad y las propiedades estructurales de este complejo, incluyendo su electrophilicidad y estabilidad térmica.
- Para comparar el comportamiento del complejo de molibdeno con su análogo de tungsteno.
Principales métodos:
- Síntesis de Cp*Mo(NO)Me(2) a través de la metátesis de los ligandos de cloro utilizando metillitio.
- Caracterización mediante espectroscopia de IR y RMN ((15) N / ((13) C).
- Reacciones con bases de Lewis e hidrólisis para determinar la electrophilicidad y la estabilidad.
Principales resultados:
- Cp*Mo(NO)Me(2) se sintetizó en un rendimiento del 75% y existe como monómero en solución, pero forma dímeros/oligómeros en estado sólido.
- El complejo es altamente electrófilo y se somete fácilmente a la acidólisis.
- La inestabilidad térmica conduce a la isomerización a una forma oxo (imido), un proceso más rápido en el complejo de tungsteno análogo.
Conclusiones:
- Cp*Mo(NO)Me(2) es un valioso, aunque inestable, compuesto organometálico con electrophilicidad significativa.
- La vía de isomerización observada pone de relieve la naturaleza dinámica de los ligandos de nitrosilo en los complejos organometálicos.
- Los estudios comparativos con análogos de tungsteno proporcionan una visión más profunda de las tendencias periódicas en la reactividad.
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