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El alquil ((amino) carbeno cíclico estabilizó el biradical del tetracloruro de disilicio

Kartik Chandra Mondal¹, Birger Dittrich, Bholanath Maity

¹Institut für Anorganische Chemie, Georg-August-Universität , Tammannstraße 4, 37077 Göttingen, Germany.

Journal of the American Chemical Society

|June 20, 2014

Resumen

Los investigadores sintetizaron y estabilizaron la esquiva molécula Si2Cl4 como un biradical sencillo utilizando alquil ((amino) carbeno cíclico. Este avance permite el aislamiento y almacenamiento de este compuesto de silicio previamente hipotético.

Área de la Ciencia:

Química del organosilicio Química del organosilicio
Química de los carbenos La química de los carbenos
Química computacional es la química computacional.

Sus antecedentes:

Se predijo teóricamente que la formación de tetracloruro de disileno (Si2Cl4) a partir del dicloruro de silicio (SiCl2) sería exotérmica.
Si2Cl4 ha permanecido como una molécula hipotética, nunca sintetizada o aislada experimentalmente.
Los carbenos cíclicos alquilo-amino son conocidos por su capacidad para estabilizar las especies reactivas.

Objetivo del estudio:

Para sintetizar y aislar experimentalmente las especies de Si2Cl4.
Para estabilizar el Si2Cl4 utilizando ligandos cíclicos de alquilo (amino) carbenos.
Para investigar la estructura electrónica y la unión del compuesto Si2Cl4 estabilizado.

Principales métodos:

Síntesis de un nuevo compuesto utilizando dos ligandos cAAC y Si2Cl4.4.
Caracterización del compuesto sintetizado para la estabilidad, aislamiento y almacenamiento.
Cálculos teóricos para aclarar la estructura electrónica y las propiedades de unión.

Principales resultados:

Síntesis y aislamiento exitosos de las especies estabilizadas de Si2Cl4, denotadas como (Cy-cAAC·) 2Si2Cl4.4.
El compuesto es estable, aislable y almacenable a temperatura ambiente bajo una atmósfera inerte.
Los estudios computacionales confirmaron un estado básico biradical singlet con electrones no apareados deslocalizados en cada átomo de carbono de carbeno con espines opuestos.

Conclusiones:

La molécula de Si2Cl4 puede estabilizarse empleando ligandos cíclicos de alquilo (amino) carbeno.
El compuesto estabilizado exhibe un carácter biradical individual, proporcionando información sobre la química biradical basada en silicio.
Este trabajo abre caminos para el estudio experimental de compuestos de silicio previamente inaccesibles.

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