5 years ago

Hydrogen Atom Abstraction Thermodynamics of a μ-1,2-Superoxo Dicopper(II) Complex

Hydrogen Atom Abstraction Thermodynamics of a μ-1,2-Superoxo Dicopper(II) Complex
Can-Jerome Günes, Nicole Kindermann, Sebastian Dechert, Franc Meyer
Pyrazolate-based μ-1,2-peroxo dicopper(II) complex 1 undergoes clean 1e oxidation at low potential (−0.59 V vs Fc/Fc+) to yield the rather stable μ-1,2-superoxo dicopper(II) complex 3, which was characterized by spectroscopic methods (ν̃(O–O) = 1070 cm–1, Δ(18O–16O) = −59 cm–1) and analyzed by DFT calculations. 3 is also formed via H-atom abstraction from the corresponding μ-1,1-hydroperoxo dicopper(II) complex 2, while 3 itself is able to abstract H-atoms from weaker X–H bonds such as TEMPO-H to re-form 2. Kinetic and thermodynamic analyses evidence a concerted proton–electron transfer pathway for these processes. The thermodynamic square scheme reveals a bond dissociation free energy of 71.7 ± 1.1 kcal mol–1 for the hydroperoxo OO–H bond of 2.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b05722

DOI: 10.1021/jacs.7b05722

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