The oxidation of tetramethylphenylenediamine (TMPD) with (salen)CrVO+ generates initially the 2-electron product TMPD2+, followed by the reaction with excess TMPD to yield the radical cation, TMPD˙+. The kinetics of both TMPD/(salen)CrVO+ and TMPD/TMPD2+ reactions are acid-dependent, with TMPD being the most reactive form, and the doubly protonated TMPDH22+ exhibiting no discernible reactivity toward either (salen)CrVO+ or TMPD2+. The specific rate constants for the individual reactions are: TMPD/(salen)CrVO+, k = (6.28 ± 0.50) × 109 M−1 s−1, TMPDH+/(salen)CrVO+, (3.89 ± 0.31) × 105, TMPD/TMPD2+, (7.61 ± 0.42) × 108, and TMPDH+/TMPD2+, (3.46 ± 0.22) × 104.
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