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Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry

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De Si (II) a Si (IV) y hacia atrás: activación de enlace carbono-carbono intramolecular reversible por un iminosileno

Daniel Wendel¹, Amelie Porzelt¹, Fabian A D Herz¹

¹WACKER-Chair of Macromolecular Chemistry, ∥WACKER-Institute of Silicon Chemistry, ‡Catalysis Research Center, Technische Universität München , Lichtenbergstraße 4, 85748 Garching bei München, Germany.

Journal of the American Chemical Society

|June 8, 2017

Resumen

Este estudio informa de un nuevo compuesto de silicio que puede transformarse de manera reversible entre los estados Si (II) y Si (IV). Esta reversibilidad permite la activación de moléculas pequeñas como el dióxido de carbono y el hidrógeno, abriendo nuevas vías en la química del silicio.

Área de la Ciencia:

Química del silicio orgánico
Química del grupo principal
Catálisis

Sus antecedentes:

La reversibilidad es crucial en la catálisis, particularmente para los compuestos de silicio de baja valencia.
La interacción de la adición oxidativa y la eliminación reductora es clave para los ciclos catalíticos en la química de grupo principal.

Objetivo del estudio:

Informar sobre un nuevo iminosilisileno acíclico (Si ((II)) que se somete a una inserción intramolecular en un enlace C=C.
Investigar la reversibilidad del compuesto de Si (IV) resultante (silepin).
Explorar la utilidad de la silepina como un equivalente sintético del sileno para la activación de moléculas pequeñas.

Principales métodos:

Síntesis y caracterización del iminosilisileno y sus derivados.
Espectroscopia UV-vis para el estudio de la reversibilidad térmica.
Cálculos de la teoría funcional de la densidad (DFT).
Reacciones con moléculas pequeñas (CO2, C2H4, H2).

Principales resultados:

Se sintetizó un iminosilisileno (1) acíclico y se formó fácilmente una silepina (2) a través de la inserción intramolecular C=C.
La silepina Si (IV) (2) mostró una fácil transformación térmica de nuevo a Si (II), confirmada por UV-vis, DFT y aislamiento de un adducto de silenoboro (3).
Silepin (2) activó el CO2 para formar el primer complejo de carbonato de silicio monomérico de cuatro coordenadas (4).
Las reacciones con etileno e hidrógeno producen silirano (5) y un dihidruro de Si (IV) (6), respectivamente.

Conclusiones:

El compuesto de silicio informado exhibe un comportamiento reversible de Si (II) /Si (IV), crucial para las aplicaciones catalíticas.
Silepin sirve como un versátil equivalente sintético para el silileno en la activación de moléculas pequeñas en condiciones suaves.
Este trabajo amplía el alcance de la química de silicio de baja valencia y la activación de moléculas pequeñas.

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