OP-II-3

OP-I-14THE EXPERIENCE OF KINETIC MODEL DESIGNFOR CYCLOHEXENE CATALYTIC OXIDATION BY p-QUINONESIN THE CATIONIC PALLADIUM (ll) COMPLEXES SOLUTIONS.A NEW WAY TO CYCLOHEXANONETemkin O.N., Katsman E.A., Bruk L.G., Zakharova D.S.Moscow State Academy of Fine Chemical Technology, Vernadsky Pr. 86,Moscow, 119571, Russia, e-mail: olegtemkin@mail.rup-Quinones (Q) play an important role in electron and proton transfer in oxidativetransformations in biochemical reactions and in chemical oxidative catalysis withmetal complexes. They act a) as oxidants of the metal catalysts reduced forms, b) asoxidants and catalysts of the intermediates demetallization steps and c) as ligandsfor the active catalyst forms stabilization [1,2]. It is known that cationic Pd(ll)complexes in water and water-organic solvents are very active catalysts of α-olefinesand cycloolefines oxidation to ketones by p-quinones [3-6]. After the new technologydesigned by Asahi Com. for the cyclohexene (CH) production from benzene the newprocess of the cyclohexanone synthesis by CH oxidation by Q and oxygen comesinto particular interest. The unexpected kinetic behaviour of the system: Pd(OAc) 2 –HClO 4 – Q –CH 3 CN – H 2 O [7,8] makes this reactions an interesting object formechanistic studies and kinetic model design too. The results of kinetic study of CHoxidation in this system are presented InFig. 1C s , Mthis report.0.15A BThe preliminary investigations showed0.12[7] the existence of two parts on kinetic0.0930.06curves (Fig. 1) – fast (A) and slow (B). The20.03initial reaction rates increase up to10t, min maximum with [HClO 4 ] 0 and [Q] 0 growth,0 10 20 30 40 50 60depend on the Q nature and increase withPd concentration according to the S-type curve. The kinetic data are not described bythe known kinetic model of one route reaction of the Wacker-process in the quasisteady-stateconditions [9]. The TEM experiments showed the absence of thecolloids and nanoclusters with the size more then 1 nm.To explain the presence of A and B parts on the kinetic curves, the weakdependence of the reaction rates on the substrate and palladium concentrations on62