O2 Activation by a Coordinated -NH- Function: Hydrogen Atom Transfer and Aromatic Ring Oxidation.

Abstract

Herein, we disclose a unique method of oxidation of a 1,4-naphthoquinone ring in air. We report that (1,4-naphthoquinone)-NH-N=C(OH)Ph (H3L) coordinated to octahedral ruthenium(II) and osmium(II) ions activates an 3O2 molecule spontaneously. Hydrogen atom transfer (HAT) from the -NH- function of H3L to 3O2 and subsequent (2e + 2H+) oxidation forming (1,3,4-trioxonaphthalen)=N-N=C(OH)Ph (HLOX) have been established. The H3L → HLOX transformation occurs via (3-hydroperoxy-1,4-naphthoquinone)=N-N=C(O-)Ph (HLOOH-) as an intermediate. The primary step is HAT generating H2L•- and hydroperoxide (OOH•) radicals. H2L•- is delocalized over the aromatic ring and incites coupling reactions via ortho carbon and produces coordinated HLOOH-. In solution, the homolytic cleavage of the peroxo bond leads to aromatic ring oxidation, affording LOX-. Ruthenium(II) and osmium(II) complexes of the types [MII(H2L-)(PPh3)2X], [MII(HLOOH-)(PPh3)2X], and trans-[MII(LOX-)(PPh3)2X] were successfully isolated in good yields. Notably, the cyclic voltammograms of all of the complexes exhibit reversible anodic waves due to MIII/MII redox couples. The rate constants of the [MII(H2L-)(PPh3)2X] → [MII(HLOOH-)(PPh3)2X] conversions determined by time-driven UV-vis spectroscopy in dry CH2Cl2, wet CH2Cl2, and D2O wet CH2Cl2 in air at 298 K follow the order > > . It is established that the rate constants are dependent on the 3O2 content of the solution but not on the concentration of the complex.