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Kinetics and mechanism of the reaction of allyl chloride with trichlorosilane catalyzed by carbon‐supported platinum
Author(s) -
Marciniec Bogdan,
Maciejewski Hieronim,
Duczmal Wojciech,
Fiedorow Ryszard,
Kityński Dariusz
Publication year - 2003
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.402
Subject(s) - trichlorosilane , chemistry , platinum , catalysis , hydrosilylation , kinetics , reaction rate constant , activation energy , reaction mechanism , organic chemistry , silicon , physics , quantum mechanics
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 ( k obs , k 1 and k 2 from the model of competitive reactions) and activation energy ( E a = 11 kcal mol −1 (46.2 kJ mol −1 )) were determined. The data obtained point to a non‐linear dependence of k obs 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 C 1 which can decompose in two directions according to the Chalk–Harrod mechanism. Copyright © 2003 John Wiley & Sons, Ltd.