Kim Jee Eon, Carroll Patrick J, Schelter Eric J
P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104, USA.
Chem Commun (Camb). 2015 Oct 18;51(81):15047-50. doi: 10.1039/c5cc06052d.
We report the synthesis of 1,3-bis[(2′-tertbutyl)hydroxyaminophenyl]benzene (H2arene-diNOx) and its metal complexes, Ce(arene-diNOx)2 (1) and [(py)2K(18-crown-6)][La(arene-diNOx)2] (2). Electrochemical studies demonstrated that the H2arene-diNOx, bidentate nitroxide ligands significantly stabilized the Ce(IV/III) redox couple to −1.74 V versus Fc/Fc(+). Moreover, a reversible oxidation wave was observed for 1 at −0.37 V, leading to a novel, stable redox-active nitroxide ligand. DFT calculations confirmed that the observed oxidation is assignable to one of the nitroxide groups.
