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Formation and Redox Reactions of Some S-N and Se-N Three-electron-bonded Intermediates (CROSBI ID 483495)

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Asmus, Klaus-Dieter ; Bonifačić, Marija Formation and Redox Reactions of Some S-N and Se-N Three-electron-bonded Intermediates // Book of Abstracts / Glas, R.L. (ur.). Flagstaff (AZ): Northern Arizona University, 2002. str. 52-52-x

Podaci o odgovornosti

Asmus, Klaus-Dieter ; Bonifačić, Marija

engleski

Formation and Redox Reactions of Some S-N and Se-N Three-electron-bonded Intermediates

Selenomethionine oxide (MetSeO) can be reduced faster and more efficiently than its sulfur analogue, methionine sulfoxide. This has been quantified by time-resolved pulse radiolysis experiments.1 MetSeO reacts with one-electron reductants, such as eaq- (k = 1.2×1010 M-1 s-1), CO2&middot ; - (k= 5.9×108 M&#8211 ; 1 s&#8211 ; 1) and (CH3)2C&middot ; OH (k =3.5×107 M&#8211 ; 1 s&#8211 ; 1) forming a transient selenium-nitrogen coupled zwitterionic radical with the positive charge at an intramolecularly formed Se\N 2s/1s* three-electron bond. The latter is characterized by an optical absorption with lmax 375 nm, and a half-life of about 70 ms. A corresponding transient with a S\N 2s/1s* three-electron can be expected upon reduction of methionineoxide. However, the MetSO reduction is too slow and the follow-up reaction too fast for experimental verification. The Se\N and S\N radical species are, however, easily generated upon &middot ; OH or N3&middot ; radical-induced oxidation of selenomethionine (MetSe) and methionine (MetS), respectively. In contrast to the selenium analogue the S\N radical derived from methionine has only a very short lifetime (t1/2 &#8776 ; 200 ns). The lifetimes of Met(Se\N) and Met(S\N) are controlled by decarboxylation of these species. The three-electron bonded radicals constitute the one-electron redox intermediate between the two oxidation states, MetSeO/MetSO and MetSe/MetS. As shown for a number of S\N transient radicals from various organic sulfides, these species exhibit both reducing as well as oxidizing properties. By comparison, the S\N species are, however, the slightly better oxidants (weaker reductants) than the Se\N species.

free radicals; redox reactions

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Podaci o prilogu

52-52-x.

2002.

objavljeno

Podaci o matičnoj publikaciji

Book of Abstracts

Glas, R.L.

Flagstaff (AZ): Northern Arizona University

Podaci o skupu

20th International Symposium on the Organic Chemistry of Sulfur

predavanje

14.07.2002-20.07.2002

Flagstaff (AZ), Sjedinjene Američke Države

Povezanost rada

Kemija