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Reacción de Cp* (Cl) M (Dieno) (M = Ti, Hf) con los isonitriles

Travis N Valadez¹, Jack R Norton¹, Michelle C Neary¹

¹Department of Chemistry, Columbia University, New York, New York 10027, United States.

Journal of the American Chemical Society

|August 1, 2015

Resumen

Los complejos de dieno de titanio y hafnio reaccionan con los isonitriles para formar nuevas estructuras de diimina y diazahaflaciclopentano. Estas reacciones revelan nuevas vías en la química organometálica y reordenamientos moleculares complejos.

Área de la Ciencia:

Química organometálica
Química de coordinación
Investigación de la catálisis

Sus antecedentes:

Los isonitriles son compuestos orgánicos versátiles con una reactividad única.
Los complejos de titanio y hafnio con dienos son conocidos por su potencial catalítico.
Comprender la reactividad de estos complejos es crucial para desarrollar nuevas metodologías sintéticas.

Objetivo del estudio:

Investigar la reacción de los isonitriles con los complejos de dieno de titanio y hafnio.
Caracterizar los complejos organometálicos resultantes.
Explorar las vías mecanicistas de estas transformaciones.

Principales métodos:

Síntesis de complejos de dieno de titanio y hafnio.
Reacción de los complejos con varios isonitriles.
Caracterización de productos mediante técnicas de cristalografía y espectroscopia de rayos X.

Principales resultados:

El complejo de titanio Cp*(Cl) Ti(2,3-dimetilbutadieno) reaccionó con los isonitriles para producir complejos de η(1),η(2) -diimina.
El complejo de diimina de titanio se fragmentó en condiciones específicas para formar un derivado de ciclopento-3-enimina.
El análogo de hafnio Cp*(Cl) Hf(2,3-dimetilbutadieno) reaccionó con 2,6-dimetilfenil isonitrile para formar un 2,5-diazahaflaciclopentano con una interacción σ-ciclopropano.

Conclusiones:

Los isonitriles experimentan diversas reacciones con complejos de dieno de titanio y hafnio, que conducen a estructuras organometálicas únicas.
Las vías de fragmentación y ciclización observadas destacan la compleja reactividad de estos complejos metálicos.
El estudio proporciona nuevos conocimientos sobre la química de coordinación de los primeros metales de transición con moléculas orgánicas insaturadas.

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