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La atropisomerización, la activación C-H y la sustitución disociativa en algunos complejos de bifenilo platino (II)

Maria Rosaria Plutino¹, Luigi Monsu' Scolaro, Alberto Albinati

¹Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina - Salita Sperone, 31 - Vill. S. Agata - 98166 Messina, Italy.

Journal of the American Chemical Society

|May 20, 2004

Resumen

Este estudio introduce un nuevo compuesto dinuclear de platino (II), [Pt (II) ], [micro-SEt (II) ], [Pt (II) ], [micro-SEt (II) ], [Pt (II) ], [micro-SEt (II) ], [Pt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [Hbph (Hb) ], que sirve como precursor de varios complejos mononucleares de platino. La investigación detalla su síntesis, caracterización y reactividad, incluidos los procesos de atropisomerización y activación de C-H.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
Coordinación Química de la Coordinación
Química del platino en la química del platino

Sus antecedentes:

La síntesis de nuevos complejos de platino con perfiles estructurales y de reactividad únicos es crucial para el avance de la química de coordinación.
Comprender el comportamiento de los compuestos dinucleares de platino (II) proporciona información sobre las interacciones metal-metal y los procesos catalíticos.

Objetivo del estudio:

Para sintetizar y caracterizar un nuevo compuesto dinuclear de platino (II), [Pt (II) ] [micro-SEt (II) ] [Hbph (IV) ] .
Para investigar la reactividad de este complejo dinuclear, incluyendo la atropisomerización y la ciclometalización.
Explorar su utilidad como precursor de los complejos mononucleares de platino (II).

Principales métodos:

Reacción del 2,2'-dilithiumbiphenyl con el cis-[PtCl(2)(SEt(2))(2)].
Espectroscopia de RMN y cálculos de mecánica molecular (MMFF) para la caracterización.
Estudios cinéticos utilizando transferencia de magnetización por RMN y espectroscopia UV/vis.

Principales resultados:

Se sintetizó y caracterizó un nuevo complejo dinuclear de platino (II), [Pt (II) ], [Pt (II) ], [micro-SEt (II) ], [Pt (II) ], [micro-SEt (II) ], [Pt (II) ], [micro-SEt (II) ], [Pt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-SEt (II) ], [micro-Hbph (Hb) ], ]).
El complejo se somete a atropisomerización y activación de C-H, dando como resultado un complejo dinuclear de platino (II) con un bifenilo dianio y bifenilo planas.
Sirve como un precursor versátil para varios complejos mononucleares eta(1)-bifenil platino(II), incluidos aquellos con ligandos bpy y fen.
Se determinaron las estructuras cristalinas de [Pt ((Hbph) ((2) ((bpy)) ] y [Pt ((Hbph) ((2) ((phen)) ], revelando isómeros de la cabeza a la cola.
Los estudios cinéticos indican un mecanismo de activación disociativo para el intercambio y la sustitución de ligandos.

Conclusiones:

El complejo dinuclear de platino (II) [Pt (II) ] es un valioso intermediario sintético.
La atropisomerización observada y la activación de C-H resaltan el comportamiento dinámico de estos complejos de platino.
El estudio proporciona una comprensión completa de la síntesis, caracterización y reactividad de estos sistemas de platino, con implicaciones para la catálisis y la ciencia de los materiales.

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