Peroxides reaction with organometallic compounds

T. G. Brihnka and V. A. Shushunov, Reactions of Organometallic Compounds with Ouygen and Peroxide, CRC Press, Inc., Cleveland, Ohio, 1969, pp. 184-185. 

For a monograph, sec Brilkina Shushunov Reactions of Organometallic Compounds with Oxygen and Peroxides, CRC Press Boca Raton, FL, 1969. For a review, sec Wardcll Paterson, in Hartley Palai, Ref. I. vol. 2, 1985 pp. 219-338. pp. 311-316. 

Lawesson Yang J. Am. them. Soc. 1959,81, 4230 Lawesson Frisell Denney, Denney Tetrahedron 1963, 19, 1229. For a monograph on the reactions of organometallic compounds with peroxides, see Ref. 298. For a review, see Razuvaev Shushunov Dodonov Brilkina, in Swern Organic Peroxides, vol. 3 Wiley New York. 1972, pp. 141-270. 

Brilkina T.G, Shushunov V.A, Reactions of Organometallic Compounds with Oxygen and Peroxides, Nauka, Moscow, 1966... 

Berlin, L.E. (Tr. Nauch. Inst. Moscow 1958 49, cited in Brilkina, T.G. Shushunov, V.A., Reactions of Organometallic Compounds with Oxygen and Peroxides, Iliffe, London 1969, p. 158). 

Razuvaev, G.A. Shushunov, V.A. Oodonov, V.A. Brilkina, T.G. (in Swern, D., Organic Peroxides, Vol. 3, Reactions of Organometallic Compounds with Organic Peroxides, WIley-Interscience, New York 1972, pp. 141/270). 

Finally, a mention should be made about the one peroxo system which will become more and more dominant the organometallic oxides of rhenium(VII). Such compounds have been found to be of outstanding catalytic activity for a number of oxygen transfer reactions with hydrogen peroxide.92 The best studied complex is methyltrioxorhenium(VII) (MTO) and its congeners. Figure 2.32 illustrates its synthesis. Epoxidation, aromatic oxidation and halide oxidation with these complexes have been studied with hydrogen peroxide and shown to be remarkably efficacious. 

Borsini, et al.,f ] reported the use of a redox catalyst system for the polymerization of ethylene and chlorotrifluoroethylene. One advantage of this catalyst system was that it permitted operation at lower temperatures than with peroxides. It allowed production of polymers with a linear chain, an orderly distribution of the asymmetric points. This process had favorable economics due to the possibility of the recovery of the catalyst, followed by its oxidation and recycle. The catalytic system was comprised of an organometallic compound and tetravalent cerium salt in quantities ranging from 0.01 to 2 of the former and 0.001 to 1 of metallic cerium part by weight per hundred parts by weight of the monomer mixture. This catalyst allowed the polymerization reaction to be conducted in the range of -60 to 20°C. Examples of the catalytic system include Pb(C2H5)4 and (NH4)2Ce(N03)g. 

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