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Tripleto de fenilarsinideno y su oxidación a dioxofenilarzina

Weiyu Qian¹, Peter R Schreiner¹, Artur Mardyukov¹

¹Institute of Organic Chemistry, Justus Liebig University, Giessen 35392, Germany.

Journal of the American Chemical Society

|May 26, 2023

Resumen

Los investigadores sintetizaron y caracterizaron el fenilarsinideno triplet, un intermediario altamente reactivo, utilizando el aislamiento de la matriz y la fotólisis. Este avance abre nuevas vías para el estudio de los compuestos de arsénico y su reactividad.

Área de la Ciencia:

Química organometálica
Química del grupo principal
La fotoquímica

Sus antecedentes:

Los carbenos y los nitrenos son intermedios reactivos cruciales en varios campos químicos.
Los arsinidenos sustituidos suelen ser demasiado reactivos para el aislamiento y la caracterización.
El arsinideno padre (H-As) está bien caracterizado, pero sus contrapartes sustituidas siguen siendo escurridizas.

Objetivo del estudio:

Preparar y caracterizar un arsinideno sustituido estable.
Para investigar la reactividad del fenilarsinideno con el oxígeno molecular.
Explorar la isomerización fotoquímica de los compuestos arsénico-oxígeno resultantes.

Principales métodos:

Aislamiento de la matriz de la diazida fenilarcénica en argón.
Fotólisis del precursor para generar el fenilarsinideno triple.
Caracterización espectroscópica mediante espectroscopia infrarroja y UV/vis.
Etiquetado de isótopos y estudios computacionales (B3LYP/def2-TZVP) para su validación.

Principales resultados:

Preparación y caracterización exitosas del fenilarsinideno triplet.
Formación de una nueva anti-dioxifenilarcina tras la reacción con el oxígeno molecular.
Isomerización fotoquímica de la anti-dioxifenilarcina a la dioxofenilarcina.
Resultados experimentales validados por análisis computacional y etiquetado de isótopos.

Conclusiones:

El fenilarsinideno tripleto puede estabilizarse y caracterizarse mediante técnicas de aislamiento de matriz.
La reactividad del fenilarsinideno con el oxígeno conduce a nuevos compuestos arsénico-oxígeno.
La fotoquímica proporciona una ruta para isomerizar estos nuevos óxidos de arsénico.

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