from first principles PP-I-1

PP-II-5Mechanistic Scenarios for Homogeneous Catalytic Alkanes OxidationChepaikin E.G. 1 , Bezruchenko A.P. 1 , Menchikova G.N. 1 , Moiseeva N.I. 2 , Gekhman A.E. 21 Institute of Structural Macrokinetics and Materials Science RAS, Chernogolovka,Moscow region, Russia2 N.S. Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow, Russiagrig@ism.ac.ru, echep@ism.ac.ruDirect oxidation of alkanes C 1 -C 4 to the basic petrochemical products is a promising area ofnatural and associated petroleum gas processing. It is related to the problem of the C–H bondof alkanes as well as dioxygen activation [1].We used the following approaches to the design of catalytic systems [2,3]:(i) Alkanes are activated by compounds of platinum group metals.(ii) The reducing agent (CO, H 2 ) and a cocatalyst are introduced to activate dioxygen.The cocatalyst in the reduced form promotes the dioxygen transfer into the twoelectronoxidants.(iii) The compounds of platinum metals activate also the reducing agent and catalyzeregeneration of the cocatalyst.In accordance with the above-listed points, we developed the following catalytic systems:RhCl 3 / HI – I 2 – HOI / NaCl, RhCl 3 / Cu(I) – Cu(II) or Fe(II) – Fe(III) / NaCl, PdX 2 L-L /Cu(I) – Cu(II) , (X = Cl, Br; L-L = ,- bipy, o-phen) and also studied some aspects of themechanisms of C 1 -C 4 alkanes oxidation. Rhodium peroxocomplexes are mainly activeintermediates.We acknowledge financial support of this work by the Russian Foundation for BasicResearch, (RFBR 09-03-00387 and 12-03-00458) and the Program of Fundamental Researchof the Presidium of RAS No.3.Referenses:[1] Shilov A.E., Metal Complexes in Biomimetic Chemical Reactions, (1994), CRC Press, BocaRation; New-York.[2] Chepaikin E.G., Russ. Chem. Rev., (2011), 8, (4) p. 363.[3] Chepaikin E.G., Bezruchenko A.P., Boiko G.N., Gekhman A.E., Moiseev I.I., Kinet. and Catal.,(2006), 47, (1), p. 12.136