Formation of 1,10-Phenanthroline‑<i>N</i>,<i>N</i>′‑dioxide under Mild Conditions:
The Kinetics and Mechanism of the Oxidation of 1,10-Phenanthroline
by Peroxomonosulfate Ion (Oxone)
This
paper confirms the unexpected formation of 1,10-phenanthroline-<i>N</i>,<i>N</i>′<i>-</i>dioxide (phenO<sub>2</sub>) when 1,10-phenanthroline (phen) is oxidized by peroxomonosulfate
ion (PMS) in a neutral aqueous solution. The kinetics of oxidation
of phen by PMS features a complex pH dependence. In 1.00 M H<sub>2</sub>SO<sub>4</sub>, 1,10-phenanthroline-mono-<i>N</i>-oxide
(phenO) is the sole product of the reaction. The rate of the N-oxidation
is highly dependent on pH with a maximum at pH ∼6.7. The formation
of phenO occurs via two parallel pathways: the rate constant of the
oxidation of phen (<i>k</i> = 3.1 ± 0.1 M<sup>–1</sup> s<sup>–1</sup>) is significantly larger than that of Hphen<sup>+</sup> [<i>k</i> = (4.1 ± 0.3) × 10<sup>–3</sup> M<sup>–1</sup> s<sup>–1</sup>] because the two N atoms
are open to oxidative attack in the deprotonated substrate while an
internal hydrogen bond hinders the oxidation of the protonated form.
With an excess of PMS, four consecutive oxidation steps were found
in nearly neutral solutions. In the early stage of the reaction, the
stepwise oxidation results in the formation of phenO, which is converted
into phenO<sub>2</sub> in the second step. The formation of phenO<sub>2</sub> was confirmed by <sup>1</sup>H NMR and ESI-MS methods. The
results presented here offer the possibility of designing an experimental
protocol for preparing phenO<sub>2</sub>