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Uno para encontrarlos a todos: una ruta general a las especies de Ni (I) -fenolato

Alessandro Bismuto¹, Patrick Müller¹, Patrick Finkelstein¹

¹Laboratorium für Organische Chemie, ETH Zürich, Vladimir-Prelog-Weg 3, HCI, 8093 Zürich, Switzerland.

Journal of the American Chemical Society

|July 12, 2021

Resumen

Los investigadores desarrollaron un nuevo método general para sintetizar diversos complejos de níquel, superando las limitaciones en la catálisis del níquel. Este avance permite el acceso a nuevas especies de níquel para el desarrollo de nuevas reacciones catalíticas.

Área de la Ciencia:

Química organometálica
Catálisis homogénea
Química del níquel

Sus antecedentes:

La catálisis del níquel ofrece una reactividad única más allá de los metales nobles.
El progreso en la catálisis del níquel se ve obstaculizado por la falta de precursores accesibles del níquel.
El acceso limitado a especies de níquel bien definidas limita el desarrollo de nuevas reacciones catalíticas.

Objetivo del estudio:

Establecer una ruta sintética simple y general para una variedad de complejos de níquel.
Para superar la escasez de precursores de níquel para la investigación catalítica.
Permitir el descubrimiento de nuevas reacciones catalíticas basadas en níquel y conocimientos mecanicistas.

Principales métodos:

Síntesis de complejos de níquel-fenolato a través de un precursor olefínico de níquel.
Caracterización mediante difracción de rayos X de un solo cristal, teoría funcional de la densidad (DFT) y espectroscopia de resonancia paramagnética de electrones (EPR).
Aislamiento de un complejo binuclear catiónico de níquel (I) -areno.

Principales resultados:

Se estableció una ruta general hacia diversos complejos de níquel-fenolato, incluidos [Ni(IPr) ((OPh*) ], [Ni ((dcype) ((OPh*) ], [Ni ((dppe) ((OPh*) ] y [Ni ((terpy) ((OPh*) ].
Se aisló un complejo binuclear catiónico de Ni (I) -areno.
Los análisis experimentales y teóricos confirmaron la estructura electrónica y el entorno de coordinación de los complejos de níquel sintetizados.

Conclusiones:

El enfoque sintético desarrollado proporciona un acceso eficiente a una amplia gama de complejos de níquel.
Este método facilita la exploración de nuevas reactividades estequiométricas y catalíticas que implican especies de níquel.
Los hallazgos ofrecen oportunidades para una aclaración mecanicista en la catálisis a base de níquel.

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