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Radical‐Initiated Dismutation of Hydrosiloxanes by Catalytic Potassium‐Graphite
Author(s) -
Frogneux Xavier,
Pesesse Antoine,
Delacroix Simon,
Ribot François,
Carenco Sophie
Publication year - 2019
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201900172
Subject(s) - hydrosilylation , dimethylsilane , chemistry , catalysis , silane , reactivity (psychology) , potassium , graphite , silicone , organic chemistry , polymer chemistry , medicine , alternative medicine , pathology
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 (KC 8 ) 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 KC 8 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.