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From silicon(II)-based dioxygen activation to adducts of elusive dioxasiliranes and sila-ureas stable at room temperature

Matthias Drieß, professor for chemistry on the Technical University Berlin and speaker of the excellent cluster “UniCat” and his colleagues report in the new online issue of “Nature Chemistry” (DOI: 10.1038/NCHEM.666) on the successful activation of dioxygen by silicon.

Dioxygen activation for the subsequent oxygenation of organic substrates that involves cheap and environmentally friendly chemical elements is at the cutting edge of chemical research. As silicon is a non-toxic and highly oxophilic element, the use of silylenes could be attractive for facile dioxygen activation to give dioxasiliranes with a SiO2–peroxo ring as versatile oxo-transfer reagents.
However, the latter are elusive species, and have been generated and studied only in argon matrices at −233 °C.

Recently, it was demonstrated that unstable silicon species can be isolated by applying the concept of donor–acceptor stabilization. We now report the first synthesis and crystallographic characterization of dioxasiliranes stabilized by N-heterocyclic carbenes that feature a three-membered SiO2–peroxide ring, isolable at room temperature. Unexpectedly, these can undergo internal oxygen transfer in toluene solution at ambient temperature to give a unique complex of cyclic sila-urea with C=O → Si=O interaction and the shortest Si=O double-bond distance reported to date.

For more information please contact:
Prof. Dr. Matthias Drieß
Technische Universität Berlin
Speaker of the excellence cluster „Unifying Concepts in Catalysis“
Tel.: 030 314-29731
E-Mail: Matthias.driess@tu-berlin.de

Sorce: Technical University of Berlin

Topic: New Materials and Chemistry

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	Common From silicon(II)-based dioxygen activation to adducts of elusive dioxasiliranes and sila-ureas stable at room temperature Matthias Drieß, professor for chemistry on the Technical University Berlin and speaker of the excellent cluster “UniCat” and his colleagues report in the new online issue of “Nature Chemistry” (DOI: 10.1038/NCHEM.666) on the successful activation of dioxygen by silicon. Dioxygen activation for the subsequent oxygenation of organic substrates that involves cheap and environmentally friendly chemical elements is at the cutting edge of chemical research. As silicon is a non-toxic and highly oxophilic element, the use of silylenes could be attractive for facile dioxygen activation to give dioxasiliranes with a SiO2–peroxo ring as versatile oxo-transfer reagents. However, the latter are elusive species, and have been generated and studied only in argon matrices at −233 °C. Recently, it was demonstrated that unstable silicon species can be isolated by applying the concept of donor–acceptor stabilization. We now report the first synthesis and crystallographic characterization of dioxasiliranes stabilized by N-heterocyclic carbenes that feature a three-membered SiO2–peroxide ring, isolable at room temperature. Unexpectedly, these can undergo internal oxygen transfer in toluene solution at ambient temperature to give a unique complex of cyclic sila-urea with C=O → Si=O interaction and the shortest Si=O double-bond distance reported to date. For more information please contact: Prof. Dr. Matthias Drieß Technische Universität Berlin Speaker of the excellence cluster „Unifying Concepts in Catalysis“ Tel.: 030 314-29731 E-Mail: Matthias.driess@tu-berlin.de Sorce: Technical University of Berlin Topic: New Materials and Chemistry	Print page Back