The radical anion CI,-, generated by flash photolysis of solutions containing CI,-, oxidizes cobalt(l1) to cobalt(i1l). At 25 "C and / = 0 . 3 ~. the rate constant is (1-4 f 0.2) x 106 I mol-l s-l (AH$ = 29 f 4 kJ mol-1 and ASS = -31 rt 10 J K-l mol-l). The reaction is inner sphere-substitution controlled, the initial product being CoCI2+ which is not labile on the time scale of the oxidation reaction.THE oxidation of halide ions to halogens and the reduction of halogens to halide ions take place in one electron-transfer steps and the radical ions X,-(X = C1, Br, or I) are important intermediates in these reactions. Rate constants (ca. 1O1O 1 mol-l s-l) and equilibrium constants (>lo5 1 mol-l) for equilibrium (1) (X = C1, x + x-+ . x,-
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