from first principles PP-I-1

PP-II-6Water-Gas Shift Reaction Catalyzed by Water Soluble Pd Complexes:Kinetics and MechanismChepaikin E.G. 1 , Bezruchenko A.P. 1 , Noskov Yu.G. 21 Institute of Structural Macrokinetics and Materials Science RAS, Chernogolovka, Russia2 United Research & Development Center, Moscow, Russiagrig@ism.ac.ru, echep@ism.ac.ruThere are some advantages when carrying out water-gas shift reaction (WGSR) in liquidphase as compared with gas phase because equilibrium constant is rather high even at100 o -200 o C [1]. Previously we developed an efficient water-soluble catalyst for WGSR basedon Pd complexes with diphenyl-m-sulphophenyl phosphine (PPh 2 PhS) [2].In this paper we report the results of a study of the kinetics of WGSR catalyzed byPdBr 2 (PPh 2 RhS) 2 and consider probable mechanisms.The following scheme is the best consistent with the kinetic data from a number of schemesconsidered:H +H-Pd 2+ (L - )(LH)X4CO 2H-Pd 2+ (L - ) 2 LHO6HO-C-Pd 2+ (LH) 2 XPd 0 (L - )(LH)3 26 *COHO-Pd 2+ L - (LH)X 22L - =Ph 2 P-C 6 H 4 -SO - 3 (m)X -L -H +H-Pd 2+ (LH) 2 X5X - H 2H 2 OPd 2+ (L - )(LH)X 21X -LH=Ph 2 P-C 6 H 4 -SO 3 H(m)References:[1] E.G. Chepaikin, M.L. Khidekel, Koordinatzionnaya Khimiya, 8, (1982), p. 1011.[2] E.G. Chepaikin, A.P. Bezruchenko, E.N. Sal`nikova, M.L. Khidekel, Int. Symp. on HomogeneousCatalysis (ISHC), Leningrad, (1984), Abstracts, v. 4, p. 137.137