Dimethylselenide as a probe for reactions of halogenated alkoxyl radicals in aqueous solution. Degradation of dichloro- and dibromomethane.
Using pulse radiolysis and steady-state gamma-radiolysis techniques, it has been established that, in air-saturated aqueous solutions, peroxyl radicals CH 2HalOO (*) (Hal = halogen) derived from CH 2Cl 2 and CH 2Br 2 react with dimethyl selenide (Me 2Se), with k on the order of 7 x 10 (7) M (-1) s (-1), to form HCO 2H, CH 2O, CO 2, and CO as final products. An overall two-electron oxidation process leads directly to dimethyl selenoxide (Me 2SeO), along with oxyl radical CH 2HalO (*). The latter subsequently oxidizes another Me 2Se molecule by a much faster one-electron transfer mechanism, leading to the formation of equal yields of CH 2O and the dimer radical cation (Me 2Se) 2 (*+). In absolute terms, these yields amount to 18% and 28% of the CH 2ClO (*) and CH 2BrO (*) yields, respectively, at 1 mM Me 2Se. In competition, CH 2HalO (*) rearranges into (*)CH(OH)Hal. These C-centered radicals react further via two pathways: (a) Addition of an oxygen molecule leads to the corresponding peroxyl radicals, that is, species prone to decomposition into H (+)/O 2 (*-) and formylhalide, HC(O)Hal, which further degrades mostly to H (+)/Hal (-) and CO. (b) Elimination of HHal yields the formyl radical H-C(*)=O with a rate constant of about 6 x 10 (5) s (-1) for Hal = Cl. In an air-saturated solution, the predominant reaction pathway of the H-C(*)=O radical is addition of oxygen. The formylperoxyl radical HC(O)OO (*) thus formed reacts with Me 2Se via an overall two-electron transfer mechanism, giving additional Me 2SeO and formyloxyl radicals HC(O)O(*). The latter rearrange via a 1,2 H-atom shift into (*)C(O)OH, which reacts with O2 to give CO2 and O2(*)(-). The minor fraction of H-C(*)=O undergoes hydration, with an estimated rate constant of k approximately 2 x 10(5) s(-1). The resulting HC(*)(OH)2 radical, upon reaction with O2, yields HCO 2H and H (+)/O2(*-). Some of the conclusions about the reactions of halogenated alkoxyl radicals are supported by quantum chemical calculations [B3LYP/6-31G(d,p)] taking into account the influence of water as a dielectric continuum [by the self-consistent reaction field polarized continuum model (SCRF=PCM) technique]. Based on detailed product studies, mechanisms are proposed for the free-radical degradation of CH 2Cl 2 and CH 2Br 2 in the presence of oxygen and an electron donor (namely, Me 2Se in this study), and properties of the reactive intermediates are discussed.
Institute of Physico-Chemistry, National Academy of Science of the Ukraine, Naukova Street 3a, UA-79053 L'viv, Ukraine.
Oksana
O
Makogon
Roman
R
Flyunt
Thomas
T
Tobien
Sergej
S
Naumov
Marija
M
Bonifacić
D000438:Alcohols / Q000737:chemistry*; D002623:Chemistry Techniques, Analytical / Q000295:instrumentation*; D004583:Electrons; D054879:Halogenation; D006842:Hydrocarbons, Brominated / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry; D008752:Methylene Chloride / Q000737:chemistry*; D016566:Organoselenium Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010545:Peroxides / Q000737:chemistry; D011789:Quantum Theory; D012996:Solutions; D013482:Superoxide Dismutase / Q000737:chemistry; D014867:Water / Q000737:chemistry*
D000438:Alcohols; D006842:Hydrocarbons, Brominated; D016566:Organoselenium Compounds; D010545:Peroxides; D012996:Solutions; C059688:alkoxyl radical; D014867:Water; C049375:perhydroxyl radical; D017665:Hydroxyl Radical; D008752:Methylene Chloride; D013482:Superoxide Dismutase; C027947:methylene bromide; C013503:dimethylselenide