OP-II-3

OP-I-14the slow branch of kinetic curves(Fig. 1) and the repetition of the curves C s , Mafter the addition of substrate at the0,15end of reaction (Fig. 2) the0,12Fig. 20,09discrimination of the mechanistic0,06hypotheses with a number of routes 2-5 was carried out.0,030t, min.The key features of these hypotheses0 25 50 75 100 125were the rapid reduction of initialPd(CH 3 CN) x (H 2 O) 2+ y complexes by CH into Pd 2 Q 2+ and PdQ 0 complexes, which aretrue active catalysts. The reaction scheme based on these suggestions with the best8description of experimental data includes 5-route mechanism (Fig. 3) with the additional2Pd 2Q 2+stepX 25Pd 2+72 Pd 0 Q142 3X 1PdQ 0 + Pd 2+ (9)Pd 2Q 2+The ways of transformations of the primaryintermediate - metalcarbenium ions solvated6by water molecule andFig. 3the mechanisms ofoxidative catalysis with these particles are discussed. Non-Wacker reaction mechanisms is in line with the fact that the reaction rates ratio ofC 3 H 6 and C 2 H 4 oxidations is near 40 in the acidic water solution of Pd 2+ [4].Authors thank RFBR for financial support, grant № 307-03-00315 and№ 10-03-00326.References[1]. Temkin O. N., Bruk L.G., Kinet. i Kataliz, 2003,.44, № 5, p. 601.[2]. Temkin O.N., Homogeneous Catalysis with Metal Complexes. Kinetic Aspects. М., Academkniga,2008, 918 p.[3]. Matveev K.I., Shitova N.B., Zhizhina E.G., Kinet. i Kataliz, 1976, 17, № 4, p.893.[4]. Zhizhina E.G., Shitova N.B., Matveev K.I., Kinet. i Kataliz, 1981, 22, № 6, p.1451.[5]. Backvall J.-E., Hopkins R.B., Tetrahedron Lett., 1988, 29, Iss.23, p. 2885.[6]. MillerD.G., Wayner D.D.M., J. Оrg. Chem., 1990, 55, p.2924.[7]. Temkin O.N., Bruk L.G., Petrov I.V., Zakharova D.S., Book of Abstracts, ISHC-XVl, Florence,Italy, 2008. p.P021.[8]. Temkin O.N. Bruk L.G., Zakharova D.S., Odintsov K.Yu., Katsman E.A., Petrov I.V.,Istomina O.Yu., Kinet. i Kataliz, 2010 (in print).[9]. Moiseev I.I., Levanda O.G., Vargaftik M.N. // J. Am. Chem. Soc., 1974, 96, Iss.4, p.1003.+ Pd.+ OH 263