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DIGITAL.CSIC
Doctoral thesis . 2015 . Peer-reviewed
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Desprotonación de ligandos n-heterocíclicos coordinados a fragmentos organometálicos: nuevos patrones de reactividad

Authors: Huertos, Miguel A.;

Desprotonación de ligandos n-heterocíclicos coordinados a fragmentos organometálicos: nuevos patrones de reactividad

Abstract

En la presente Memoria se estudia fundamentalmente la evolución de los productos de desprotonación de compuestos organometálicos con ligandos N-alquilimidazol (N-RIm). Los fragmentos organometálicos empleados han sido de fac-{Re(CO)3} y cis-{Mo(¿3-alilo)(CO)2} debido a que, en general, sus compuestos son fáciles de preparar y presentan una gran estabilidad. En primer lugar se han estudiado los compuestos que presentan un ligando diimina (como la 2,2'-bipiridina o la 1,10-fenantrolina) y un ligando N-RIm en posiciones mutuamente cis, y se ha encontrado que, dependiendo del metal, el producto resultante de la desprotonación puede ser un complejo 2-imidazolilo, precursor de un carbeno NH N-heterocíclico (NH-NHC) o el producto de acoplamiento C-C entre el imidazol y la diimina. La extensión de estos estudios a los derivados de Re(I) con tres ligandos imidazol da lugar a los productos de apertura de uno de los heterociclos aromáticos o a los complejos 2-imidazolilo, dependiendo de la naturaleza del sustituyente presente en el ligando imidazol. Al estudiar la desprotonación de los derivados neutros de Re(I) con dos ligandos N-RIm y triflato se produce la activación de dos ligandos imidazol, originando, después de añadir la cantidad equimolar de ácido, los correspondientes complejos bis(NH-NHC). Finalmente se han estudiado las reacciones de desprotonación de los complejos catiónicos [Re(CO)3(N-RIm)2(L)]+, donde L es un nitrilo, un isonitrilo o una fosfina. En los dos primeros casos se han obtenido los productos de activación de los ligandos insaturados, formándose metalaciclos de 5 ó 4 miembros respectivamente, mientras que con los ligandos fosfina la reactividad depende en gran medida de los sustituyentes de la misma.

Memoria presentada para optar al grado de doctor por la Universidad de Oviedo (Departamento de Química Orgánica e Inorgánica) por Miguel Ángel Huertos Mansilla.

Agradezco al Ministerio de Ciencia e Innovación por la concesión de una beca.

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Spain
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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
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