Abstract
The reduction of silver porphyrins and the demetalation of the reduced species in aqueous solutions were studied by steady-state and pulse radiolysis. Ag/sup III/TPPS is reduced to Ag/sup II/TPPS by e/sub eq//sup -/ with k = 1.0 x 10/sup 10/ M/sup -1/ s/sup -1/ Ag/sup II/TPPS is reduced by e/sub eq//sup -/ (k = 1.6 x 10/sup 10/) and by (CH/sub 3/)/sub 2/COH (k = 6 x 10/sup 8/ M/sup -1/ s/sup -1/) to Ag/sup I/TPPS. Ag/sup I/TPPS reacts with water (k = 5 x 10/sup 4/ s/sup -1/) to give HAg/sup I/TPPS and the latter also reacts with water (k = 1.3 x 10/sup 3/ s/sup -1/) to yield Ag/sup +/ + H/sub 2/TPPS as final products. H/sub 2/TPPS is also reduced by e/sub eq//sup -/ rapidly, k = 1.5 x 10/sup 10/ M/sup -1/ s/sup -1/. The anion radical (H/sub 2/TPPS)/sup -/. transfers an electron to Ag/sup II/TPPS somewhat slowly, k less than or equal to 5 x 10/sup 6/ M/sup -1/ s/sup -1/, but the process occurs efficiently under ..gamma..-radiolysis conditions.
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