Reactions of organoelement peroxides of the silicon subgroup with olefins
Review articleOpen access
Abstract:

AbstractThe kinetic and activation parameters of decomposition of silicon subgroup organoelement peroxides R3EOOR′ (where E = Si, Ge, Sn; R = Me, Et; R′ = CMe3, CMe2Ph) in olefins have been determined.It is shown by the kinetic and thermochemical method that RaEOOR′ and olefins form complexes having 1 : 1 composition. For comparison, the complexing ability of the peroxide with pyridine, triethylamine and chloroform was evaluated. The stability constants (Cs) and the enthalpies of formation (ΔH) of the complexes were estimated from enthalpy values of mixing Et3SnOOCMe3 with ligands at 298.15 K. The formation of the peroxide—ligand complex is shown to depend upon both the nature of the peroxide and the ligand basicity. The competitive reactions of organoelement oxyradicals RaEO· in olefins have been studied. The nature of the heteroelement, olefin and the reaction temperature have an influence upon the competitive ability of R3EO· to add the olefin multiple bond or react via hydrogen abstraction. The probability of the addition reaction decreases in the series: R3SiO· > RaGeO· > R3CO·. The rate of reaction of hydrogen abstraction from the olefin molecule increases in the same series.

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