title: Coordination chemistry and reactivity of a cupric hydroperoxide species featuring a proximal H-bonding substituent.
abstract: At -90 °C in acetone, a stable hydroperoxo complex [(BA)Cu(II)OOH](+) (2) (BA, a tetradentate N(4) ligand possessing a pendant -N(H)CH(2)C(6)H(5) group) is generated by reacting [(BA)Cu(II)(CH(3)COCH(3))](2+) with only 1 equiv of H(2)O(2)/Et(3)N. The exceptional stability of 2 is ascribed to internal H-bonding. Species 2 is also generated in a manner not previously known in copper chemistry, by adding 1.5 equiv of H(2)O(2) (no base) to the cuprous complex [(BA)Cu(I)](+). The broad implications for this finding are discussed. Species 2 slowly converts to a μ-1,2-peroxodicopper(II) analogue (3) characterized by UV-vis and resonance Raman spectroscopies. Unlike a close analogue not possessing internal H-bonding, 2 affords no oxidative reactivity with internal or external substrates. However, 2 can be protonated to release H(2)O(2), but only with HClO(4), while 1 equiv Et(3)N restores 2.
authors.affiliation: Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States.
authors.forename: Sunghee
authors.initials: S
authors.lastname: Kim
authors.forename: Claudio
authors.initials: C
authors.lastname: Saracini
authors.forename: Maxime A
authors.initials: MA
authors.lastname: Siegler
authors.forename: Natalia
authors.initials: N
authors.lastname: Drichko
authors.forename: Kenneth D
authors.initials: KD
authors.lastname: Karlin
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D006860:Hydrogen Bonding; D006861:Hydrogen Peroxide / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure
chemical_list: D056831:Coordination Complexes; D003300:Copper; D006861:Hydrogen Peroxide