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Complejos de níquel-cobre con puente de tiolato: un modelo binuclear para el sitio catalítico de la coenzima acetil
Rangan Krishnan1, Janis K Voo, Charles G Riordan
1Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA.
Journal of the American Chemical Society
|April 10, 2003
Resumen
Este estudio explora los complejos níquel-cobre como modelos para la acetilcoenzima A sintasa. Estos complejos se unen reversiblemente al monóxido de carbono rompiendo los puentes de tiolato.
Área de la Ciencia:
- Coordinación Química de la Coordinación
- Química organometálica Química orgánica de los metales.
- Química bioorgánica Química bioorgánica.
Sus antecedentes:
- Los iones de níquel y cobre juegan un papel crucial en las metalloenzimas.
- El sitio activo de la acetilcoenzima A sintasa contiene iones de níquel y cobre.
- Comprender la relación estructura-función de estos centros metálicos es vital.
Objetivo del estudio:
- Para sintetizar y caracterizar nuevos complejos níquel-cobre.
- Para modelar el sitio activo de la acetilcoenzima A sintasa.
- Para investigar la reactividad de estos complejos con moléculas pequeñas como el monóxido de carbono.
Principales métodos:
- Síntesis de los metaloligandos del níquel: [EtN2S2]Ni y K2[Ni(phmi) ].
- Reacción con las fuentes de cobre (((I) ([Cu ((CH3CN) 4) BF4 y [{PhTttBu) Cu]).
- Caracterización de los complejos polinucleares y binucleares de NiCu resultantes.
Principales resultados:
- Formación de complejos polinucleares con dos iones de cobre (I) puenteados por metalloligandos de níquel.
- Generación de complejos binucleares discretos de NiCu utilizando [(PhTttBu) Cu].
- Demostración de la unión reversible del monóxido de carbono a las especies binucleares a través de la ruptura del puente de tiolato.
Conclusiones:
- Los complejos de NiCu sintetizados sirven como modelos efectivos para el sitio activo de la acetilcoenzima A sintasa.
- La unión reversible de CO pone de relieve la naturaleza dinámica de los puentes de tiolato.
- Este trabajo proporciona información sobre el mecanismo de la interacción del CO con los centros de Ni-Cu.
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