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Metoxifosfinideno y óxido isomérico de metilfosfinideno
Xianxu Chu1, Yang Yang1, Bo Lu1
1College of Chemistry, Chemical Engineering and Materials Science , Soochow University , Suzhou 215123 , China.
Journal of the American Chemical Society
|October 11, 2018
Resumen
Los investigadores generaron un oxifosfinideno raro (Me-OP) y observaron su isomerización a óxido de metilfosfinideno (Me-PO). Este estudio también identificó un intermediario de nitreno utilizando métodos espectroscópicos avanzados.
Área de la Ciencia:
- Química de los organofosforados
- La fotoquímica
- Espectroscopia de aislamiento de matriz
Sus antecedentes:
- Los oxyphosphinidenes son especies reactivas de fósforo con datos experimentales limitados.
- La síntesis y caracterización de los compuestos de fósforo transitorios son un desafío.
Objetivo del estudio:
- Para generar y caracterizar el oxifosfinideno raro (Me-OP) y el óxido de metilfosfinideno (Me-PO).
- Para investigar la vía de isomerización entre Me-OP y Me-PO.
- Identificar y caracterizar un intermediario de nitreno en la química de los organofosforados.
Principales métodos:
- Fotólisis (266 nm y 193 nm) de la metoxidiazidofosfina y el metilfosforil diazido.
- Pirólisis en el vacío flash (FVP) a 700 °C.
- Aislamiento de la matriz en Ne y N2 a temperaturas criogénicas.
- Espectroscopia de infrarrojo (IR) y de resonancia paramagnética de electrones (EPR) con etiquetado 15N.
Principales resultados:
- Generación de tripletes en estado de base Me-OP a partir de MeOP ((N3) 2) mediante fotólisis o FVP.
- Observación de una isomerización sin precedentes de Me-OP a Me-PO tras la irradiación a 193 nm en matrices criogénicas.
- Generación eficiente de Me-PO a partir de MeP (O) (N3) 2 mediante fotólisis o FVP.
- Detección del elusivo intermedio de nitreno MeP ((O) ((N3) N en el estado de triplete por espectroscopia IR y EPR.
Conclusiones:
- El estudio generó y caracterizó con éxito las especies transitorias de fósforo Me-OP y Me-PO.
- Se descubrió una nueva vía de isomerización entre estas especies.
- El intermediario de nitreno proporciona nuevos conocimientos sobre los mecanismos de reacción que involucran a los compuestos de fósforo.
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