Kinetics and mechanism of styrene hydroalkoxycarbonylation catalyzed by the complex PdCl2(Ph3P)2 in the presence of butanol |
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| Authors: | Yu G Noskov A I Simonov E S Petrov |
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| Institution: | (1) Karpov Research Institute of Physical Chemistry, Russian State Scientific Center, ul. Vorontsovo pole 10, 103064 Moscow, Russia |
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| Abstract: | The single-factor experiment method was used to study the kinetics of styrene hydrobutoxycarbonylation catalyzed by the complex
PdG2(Ph3P)2 in dioxane (383 K, BuOH] = 1–8 mol/1). The rates of accumulation of the regioisomeric reaction products as empirical functions
of CO pressure and concentrations of styrene, triphenylphosphine, and the catalyst were found. The acyl complex (PhC2H4CO)PdCl(Ph3P)2 was isolated from the reaction mixture. The assumed intermediate of an alcoholate mechanism, the (BuOOC)PdCl(Ph3P)2 complex, is not formed by the reaction of PdCl2(Ph3P)2 with CO and butanol. The set of data generally corresponds to a hydride mechanism of styrene hydrocarboxylation, which includes
three key intermediates HPdCIL2-n(CO)n (n= 0–2). A change in the solvation properties of the reaction medium due to the replacement of water by butanol affects the
kinetic scheme of the process. |
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