Kinetics and mechanism of the reaction of allyl chloride with trichlorosilane catalyzed by carbon-supported platinum

• Published in: Applied organometallic chemistry Vol. 17; no. 2; pp. 127 - 134
• Main Authors: Marciniec, Bogdan, Maciejewski, Hieronim, Duczmal, Wojciech, Fiedorow, Ryszard, Kityński, Dariusz
• Format: Journal Article
• Language: English
• Published: Chichester, UK John Wiley & Sons, Ltd 01.02.2003; Wiley
• Subjects: allyl chloride; Catalysis; Catalytic reactions; Chalk-Harrod mechanism; Chemistry; Exact sciences and technology; General and physical chemistry; hydrosilylation; kinetic equation; platinum catalyst; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; trichlorosilane; Catalytic reaction; Fourier transformation; Silicon Organic compounds; Thermogravimetry; Transition metal; Hydrosilylation; Supported catalyst; Infrared spectrometry; Platinum; Chlorocarbon; Reaction mechanism; Thermal analysis; Kinetics
• ISSN: 0268-2605; 1099-0739
• DOI: 10.1002/aoc.402

The kinetics of substrate conversions in the commercially important hydrosilylation of allyl chloride with trichlorosilane, catalyzed by active carbon‐supported platinum, as well as the yields of the main product (3‐chloropropyltrichlorosilane) and by‐products (tetrachlorosilane, propyltrichlorosilane) have been studied. On the basis of the measurements performed, the pseudo first‐order rate constants (kobs, k1 and k2 from the model of competitive reactions) and activation energy (Ea = 11 kcal mol−1 (46.2 kJ mol−1)) were determined. The data obtained point to a non‐linear dependence of kobs on the catalyst amount. From the kinetic relationships, the kinetic equation was deduced. All the results of kinetic, IR spectroscopic and thermogravimetric measurements, as well as the derived kinetic equation, have confirmed the general model of consecutive–competitive reaction involving the formation of a surface complex C1 which can decompose in two directions according to the Chalk–Harrod mechanism. Copyright © 2003 John Wiley & Sons, Ltd.