What is it about?
This study investigates the oxidation of various triorganosilanes, disilanes, and polysilanes by chlorine dioxide (ClO2) in acetonitrile solution at room temperature. By identifying the reaction products (silanols, silyl chlorides, and siloxanes) and combining experimental kinetics with quantum chemical modeling (G4, G3, and SMD-M05/MG3S methods), we established the underlying reaction pathways. Depending on the substrate structure, the reaction proceeds via radical hydrogen abstraction or electron-transfer ionic intermediates.
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Why is it important?
Silanols and siloxanes are vital building blocks in organic synthesis, material science, and industrial chemistry. While chlorine dioxide (ClO2) is a widely available industrial oxidant, its fundamental reaction mechanisms with organosilicon compounds were poorly understood. Our findings demonstrate that ClO2 can cleanly oxidize Si–H and Si–Si bonds without needing heavy-metal catalysts. Furthermore, our theoretical calculations clarify how structural electronic effects dictate whether oxidation occurs through radical or ionic pathways, providing a valuable framework for designing selective metal-free oxidation reactions.
Perspectives
Exploring the dual radical and ionic reactivity of chlorine dioxide with organosilicon compounds was a compelling challenge. Revealing that silyl chlorites (R3Si–O–ClO) act as key short-lived intermediates that undergo homolytic cleavage allowed us to explain the delicate product distribution between silanols and siloxanes. We hope these mechanistic insights will encourage broader applications of environmentally friendly chlorine dioxide as a selective reagent in fine chemical synthesis and silicon chemistry.
Dr Stanislav A. Grabovskii
Ufa Institute of Chemistry of the RAS
Read the Original
This page is a summary of: Oxidation of Triorganosilanes and Related Compounds by Chlorine Dioxide, Russian Journal of General Chemistry, December 2021, Pleiades Publishing Ltd,
DOI: 10.1134/s1070363221120069.
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