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Reacciones de hidrazidos de titanio con silanos y boranos: escisión de enlaces N-N y funcionalización de átomos N

Laura C Stevenson¹, Simona Mellino¹, Eric Clot²

¹†Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Mansfield Road, Oxford OX1 3TA, U.K.

Journal of the American Chemical Society

|July 31, 2015

Resumen

Los complejos de titanio se someten a la escisión del enlace N-N con agentes sililadores o boriladores, formando nuevos ligandos de amido. Otras reacciones producen productos de borilhidrazido-hidruro y borilímido, que muestran una química diversa del titanio.

Área de la Ciencia:

Química organometálica
Complejos de titanio
Síntesis de ligandos

Sus antecedentes:

Los compuestos de titanio-nitrógeno son versátiles en la catálisis y la ciencia de los materiales.
La comprensión de la reactividad de los complejos de titanio-hidrazido es crucial para el desarrollo de nuevas metodologías sintéticas.

Objetivo del estudio:

Investigar la reactividad de los complejos de titanio con los agentes sililadores y boriladores.
Para explorar la formación de nuevas especies de amido y imido de titanio.
Informar sobre la escisión de enlaces N-N, la transferencia de átomos y las reacciones de acoplamiento deshidrogenativo.

Principales métodos:

Reacción de los complejos de titanio con Ph ((R) SiH2 (R = H, Ph) y 9-BBN.
Reacción de Cp*Ti{MeC(N(i) Pr) 2} (R = Me o Ph) con la HBPina y el 9-BBN.

Principales resultados:

Clivado reductor del enlace N ((α) -N ((β) en Ti ((N2 ((iPr) N) ((NNPh2) ((py) durante la reacción con agentes siciliantes o 9-borabiciclo[3.3.1]nonano (9-BBN).
Formación de nuevos ligandos silil-amido y boril-amido.
Síntesis de borilhidrazido-hidruro y borillimido de las reacciones Cp*Ti{MeC(N(i) Pr) 2} ((NNR2) (R = Me o Ph) con HBPin o 9-BBN.
Observación de las reacciones de transferencia y acoplamiento deshidrogenativo de los átomos N ((α) y N ((β)).

Conclusiones:

El estudio demuestra la utilidad de los complejos de titanio en las reacciones de escisión de enlaces N-N.
Se sintetizaron con éxito nuevos ligandos silil-amido y boril-amido.
Los hallazgos amplían el alcance de las transformaciones mediadas por el titanio, incluida la transferencia de átomos y el acoplamiento deshidrogenativo.

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