title: Bidentate nitroxide ligands stable toward oxidative redox cycling and their complexes with cerium and lanthanum.
abstract: 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.
authors: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104, USA. schelter@sas.upenn.edu.
authors: Jee Eon
authors: JE
authors: Kim
authors: Patrick J
authors: PJ
authors: Carroll
authors: Eric J
authors: EJ
authors: Schelter