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Complejos de nitrido neutro y de baja coordinación de vanadio
Ba L Tran1, Maren Pink, Xinfeng Gao
1Department of Chemistry and the Molecular Structure Center, Indiana University, Bloomington, Indiana 47405, USA.
Journal of the American Chemical Society
|January 19, 2010
Resumen
Nuevos complejos de vanadio-nitrido fueron sintetizados a partir de precursores de vanadio-azido. Estos complejos muestran reacciones únicas de transferencia de átomos de nitrógeno, formando nuevos ligandos y reduciendo el centro de vanadio.
Área de la Ciencia:
- Química Inorgánica La Química Inorgánica es la química inorgánica.
- Química organometálica Química orgánica de los metales.
- Coordinación Química de la Coordinación
Sus antecedentes:
- Los complejos de vanadio-nitrido son importantes en la catálisis y la ciencia de los materiales.
- La síntesis de nuevos complejos de vanadio-nitrido con números de coordinación específicos es de gran interés.
Objetivo del estudio:
- Para preparar y caracterizar complejos neutrales de cuatro coordenadas de vanadio (V) -nitrido.
- Para investigar el mecanismo de la extrusión de nitrógeno de los precursores de vanadio (III) -azido.
- Para explorar la reactividad de la fracción de vanadio-nitrido en las reacciones de transferencia de N-átomos.
Principales métodos:
- La termólisis de los precursores metastables de vanadio y azido.
- Espectroscopia de RMN multinuclear. espectroscopía de RMN multinuclear. espectroscopía de RMN multinuclear. espectroscopía de RMN multinuclear. espectroscopía de RMN multinuclear. espectroscopía de RMN multinuclear. espectroscopía de RMN multinuclear.
- Espectroscopia de infrarrojo con transformación de Fourier (FT-IR). espectroscopia de infrarrojo con transformación de Fourier.
- Estudios de etiquetado isotópico.
- Difracción de rayos X de un solo cristal.
Principales resultados:
- Sintetizó con éxito dos complejos neutrales de cuatro coordenadas de vanadio (V) -nitrido.
- Propuso un mecanismo de estado de transición ordenado y temprano para la extrusión de N (((2) que involucra marcos de ciclo de triazametales.
- Se ha demostrado una transferencia incompleta del átomo N al CO y un cianuro sustituido, formando ligandos doblados V-N=C=X.
- Se observó una reducción concomitante de 2 electrones en el centro del vanadio durante la transferencia del átomo N.
Conclusiones:
- La termólisis de los precursores de vanadio (III) -azido es una vía eficaz para los complejos de vanadio (V) -nitrido.
- El mecanismo de extrusión N(2) implica estados de transición cíclicos específicos.
- Los complejos de vanadio-nitrido pueden participar en reacciones únicas de transferencia de átomos N, lo que lleva a nuevas formaciones de ligandos y cambios redox.
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