Reversible H-Atom Abstraction from Alcohols by Thiyl Radicals: Determination of Absolute Rate Constants by Pulse Radiolysis

Abstract

Hahn-Meitner-Institut Berlin, Bereich Strahlenchemie, Glienicker Str. 100, 1000 Berlin 39, Fed. Rep. Germany

Penicillamine thiyl radicals, PenS', are shown to abstract hydrogen atoms from 2-propanol and to establish an equilibrium

PenS' + (CH₁)₂ CHOH ↔ PenSH + (CH₃)₂ COH.

The rate constants for the forward and back reaction have been determined to (1.4 ± 0.3) × 10⁴ and (1.2 ± 0.3) × 10⁸ M^-1 s^-1, respectively, by means of pulse radiolysis. The data have been obtained from various independent methods which include direct measurements and competitive schemes involving irreversible interception of the alcohol radical by electron acceptors (e.g. CCl₄. PNAP) and/or the thiyl radical by antioxidants (e.g. α-tocopherol). The results demonstrate that the reaction of carbon-centered radicals with thiols, in radiation biology commonly known as “repair” reaction, may be reversed and thus imply the possibility of thiyl radical induced biological damage.

Key Words:

• Thiyl radicals
• reversible H-atom abstraction
• alcohols
• CCl₄
• α-tocopherol
• pulse radiolysis