title: Fine-tuning the oxidative ability of persistent radicals: electrochemical and computational studies of substituted 2-pyridylhydroxylamines.
abstract: N-tert-butyl-N-2-pyridylhydroxylamines were synthesized from 2-halopyridines and 2-methyl-2-nitrosopropane using magnesium-halogen exchange. The use of Turbo Grignard generated the metallo-2-pyridyl intermediate more reliably than alkyllithium reagents. The hydroxylamines were characterized using NMR, electrochemistry, and density functional theory. Substitution of the pyridyl ring in the 3-, 4-, and 5-positions was used to vary the potential of the nitroxyl/oxoammonium redox couple by 0.95 V. DFT computations of the electrochemical properties agree with experiment and provide a toolset for the predictive design of pyridyl nitroxides.
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Justin A
authors.initials: JA
authors.lastname: Bogart
authors.forename: Heui Beom
authors.initials: HB
authors.lastname: Lee
authors.forename: Michael A
authors.initials: MA
authors.lastname: Boreen
authors.forename: Minsik
authors.initials: M
authors.lastname: Jun
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Schelter
mesh_terms: D055664:Electrochemical Techniques; D005609:Free Radicals / Q000737:chemistry; D006219:Halogens / Q000737:chemistry; D006898:Hydroxylamines / Q000138:chemical synthesis*; D008274:Magnesium / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D009603:Nitroso Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D011725:Pyridines / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D005609:Free Radicals; D006219:Halogens; D006898:Hydroxylamines; D009603:Nitroso Compounds; D011725:Pyridines; D008274:Magnesium; C034526:tert-nitrosobutane