Acid Catalysis in the Oxidation of Substrates by Mononuclear Manganese(III)-Aqua Complexes

Acids are known to enhance the reactivities of metal-oxygen intermediates, such as metal-oxo, -hydroperoxo, -peroxo, and -superoxo complexes, in biomimetic oxidation reactions. Although metal-aqua (and metal-hydroxo) complexes have been shown to be potent oxidants in oxidation reactions, acid effects on the reactivities of metal-aqua complexes have never been investigated previously. In this study, a mononuclear manganese(III)-aqua complex, [(dpaq5NO2)MnIII(OH2)]2+ (1; dpaq5NO2 = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-ylacetamidate with an NO2 substituent at the 5 position), which is relatively stable in the presence of triflic acid (HOTf), is used in the investigation of acid-catalyzed oxidation reactions by metal-aqua complexes. As a result, we report a remarkable acid catalysis in the six-electron oxidation of anthracene by 1 in the presence of HOTf; anthraquinone is formed as the product. In the HOTf-catalyzed six-electron oxidation of anthracene by 1, the rate constant increases linearly with an increase of the HOTf concentration. Combined with the observed one-electron oxidation product, anthracene (derivative) radical cation, and the substitution effect at the 5 position of the dpaq ligand in 1 on the rate constants of the oxidation of anthracene, it is concluded that the oxidation of anthracene occurs via an acid-promoted electron transfer (APET) from anthracene to 1. The dependence of the rate constants of the APET from electron donors, including anthracene derivatives, to 1 on the driving force of electron transfer is also shown to be well fitted by the Marcus equation of outer-sphere electron transfer. To the best of our knowledge, this is the first example showing acid catalysis in the oxidation of substrates by metal(III)-aqua complexes.