Radical‐Initiated Dismutation of Hydrosiloxanes by Catalytic Potassium‐Graphite

Abstract

Formation of higher‐value products from cheaper silicone precursors such as polymethylhydrosiloxane (PMHS) is a challenge for silicon chemistry. Here, we show that catalytic amount (<0.5 mol %) of potassium graphite (KC8) can be used as an efficient radical initiator for the cleavage of Si−O bonds of hydrosiloxanes. Methylsilane and dimethylsilane are quantitatively obtained from PMHS and TMDS (1,1,3,3‐tetramethyldisiloxane), respectively. Taking advantage of the high reactivity of the newly formed silane, the reduction of carbonyl functionalities with KC8 in catalytic amount was further performed. Mechanistic investigations suggest that both the dismutation of the initial hydrosiloxane and the reduction of carbonyl derivatives by hydrosilylation are initiated with a radical pathway.

Nagoya‐Medaillen: C. R. Bertozzi und M. Kanai / Clara‐Immerwahr‐Preis: S. Carenco / Adolf‐Lieben‐Vorlesung: I. Marek

“…Dieses Jahr geht der Preis an

Sophie Carenco (Sorbonne Université, Paris; Frankreich), über die in dieser Rubrik anlässlich ihrer CNRS‐Bronzemedaille 2018 berichtet wurde . Carenco hatte einen Beitrag über die radikalische Dismutation von Hydrosiloxanen im ChemCatChem ‐Themenheft “Women of Catalysis”, und sie war mit einem Full Paper über einstellbare magnetische Eigenschaften von Gadolinium‐Cer‐Oxysulfid‐Nanopartikeln auf dem Titelbild des European Journal of Inorganic Chemistry vertreten …”

Nagoya Medals: C. R. Bertozzi and M. Kanai / Clara Immerwahr Award: S. Carenco / Adolf Lieben Lectureship: I. Marek

“…This year's winner,

Sophie Carenco (Sorbonne Université, Paris; France), has been introduced in this section when she was awarded a CNRS Bronze Medal in 2018 . Carenco has reported on a radical‐initiated dismutation of hydrosiloxanes in a Communication in ChemCatChem 's Special Issue Women of Catalysis, and her Full Paper on tunable magnetic properties of gadolinium–cerium oxysulfide nanoparticles was selected for the cover of European Journal of Inorganic Chemistry …”

Meet the Women of Catalysis

“…More recently, she was awarded the Bronze Medal of CNRS, the Jean Rist Medal of SF2M and the Young Chemist Award of SCF‐DCP. She is also involved in science public outreach and published in 2012 a short book about nanomaterials and chemistry …”