Abstract
Cross-reaction rate constants k12 (22 °C) at pH 7.0 have been determined for the reduction of FeIII2 and tyrosyl-radical-containing active-R2 from E. coli ribonucleotide reductase with eight organic radicals (OR), e.g., MV•+ from methyl viologen. The more reactive OR's were generated in situ using pulse radiolysis (PR) techniques, and other OR's were generated by prior reduction of the parent with dithionite, followed by stopped-flow (SF) studies. In both procedures it was necessary to include consideration of doubly-reduced parent forms. Values of k12 are in the range 109 to 104 M-1 s-1 and reduction potentials Eo1 for the OR vary from −0.446 to +0.194 V. Samples of E. coli active-R2 also have an FeIII2 met-R2 component (with no Tyr•), which in the present work was close to 40%. From separate experiments met-R2 gave similar k12 rate constants (on average 66% bigger) to those for active-R2, suggesting that reduction of the FeIII2 center is the common rate-limiting step. A single Marcus free-energy plot of...
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