OP-II-3

OP-I-15The hydride palladium complexes are the most probable intermediates to beresponsible for coupling of reactions (1) and (3) or (4)[4,5]. These complexes may bereceived by oxidation carbon monoxide with palladium(II) (5) and ones are wellstudied catalysts for alkene hydrocarboxylation to saturated acids [8].This report deals with results of mechanistic study of conjugate process (1)+(4).Hypothetical mechanisms were discriminated using results of kinetic (includingkinetic isotop effect of changing H 2 O by D 2 O) and of nonkinetic (UV- and VIS-, IRspectroscopyof model and reaction solutions) studies. As result: the most probablemechanism includes hydride palladium complex formation in steps 5, 6 (oxidation ofCO). This complex catalyzes cyclohexene hydrocarboxylation (steps 7-10) and isoxidized by oxygen to hydrogen peroxide (steps 12,13).PdX 2 (CO) 2 + H 2 O ↔ PdX 2 (CO)(COOH 2 ) (5)PdX 2 (CO)(COOH 2 ) + CO → HPdX(CO) 2 + CO 2 + HX (6)HPdX(CO) 2 + C 6 H 10 ↔ HPdX(CO)(C 6 H 10 ) + CO (7)HPdX(CO)(C 6 H 10 ) → XPd(CO)(C 6 H 11 ) (8)XPd(CO)(C 6 H 11 ) + CO → XPdC(O)(C 6 H 11 )(CO) (9)XPdC(O)(C 6 H 11 )(CO) + H 2 O → HPdX(CO) + C 6 H 11 COOH (10)HPdX(CO) + CO ↔ HPdX(CO) 2 (11)HPdX(CO) + O 2 + СО → (CO) 2 XPdOOH (12)(CO) 2 XPdOOH + HX → PdX 2 (CO) 2 + H 2 O 2 (13)HPdX(CO) + C 6 H 10 ↔ HPdX(CO)(C 6 H 10 ) (14)2H 2 O 2 → 2H 2 O + O 2 (15)Chemical conjugation and chemical induction take place in this mechanism beingin accordance with all experimental data.Referenses[1]. Khimicheskaya entsiklopediya (Chemical encyclopaedia)// M.: Bolshaya rossiyskayaentsiklopediya, 1995, V.4, 767 p.[2]. Shilov N.A. O sopryajennikh reaktsiyakh okisleniya// M., 1905, 304 p.[3]. Boudart M.// J. Phys. Chem. 1983, V. 87, P. 2786.[4]. Bruk L.G., Abdullaeva A.S., Temkin O.N. et al.// In Abstracts 14-th Int. Symp. Homog. Catal.,Munich, 2004, PO124.[5]. Bruk L.G., Oshanina I.V., Temkin O.N. et al.// Ros. Chim. J. 2006, V. L, 4, P. 103.[6]. Bruk L.G.,Abdullaeva A.S., Timashova E.A. et al. Kinetika i Kataliz, 2010, in press.[7]. Likholobov V.A., Ermakov Yu.I. Kinetika i Kataliz, 1980, V. 21, P. 904.Financial support of RFBR, grant 08-03-00258.65