Stepwise protonation and electron-transfer reduction of a primary copper-dioxygen adduct.

ABSTRACT: The protonation–reduction of a dioxygen adduct with [LCu(I)][B(C6F5)4], cupric superoxo complex [LCu(II)(O2(•–))]+ (1) (L = TMG3tren (1,1,1-tris[2-[N(2)-(1,1,3,3-tetramethylguanidino)]ethyl]amine)) has been investigated. Trifluoroacetic acid (HOAcF) reversibly associates with the superoxo ligand in ([LCu(II)(O2(•–))]+) in a 1:1 adduct [LCu(II)(O2(•–))(HOAcF)](+) (2), as characterized by UV–visible, resonance Raman (rR), nuclear magnetic resonance (NMR), and X-ray absorption (XAS) spectroscopies, along with density functional theory (DFT) calculations. Chemical studies reveal that for the binding of HOAcF with 1 to give 2, Keq = 1.2 × 10(5) M(–1) (−130 °C) and ΔH° = −6.9(7) kcal/mol, ΔS° = −26(4) cal mol(–1) K(–1)). Vibrational (rR) data reveal a significant increase (29 cm(–1)) in vO–O (=

SUBMITTER: Peterson RL 

PROVIDER: S-EPMC3874213 | biostudies-literature | 2013 Nov

REPOSITORIES: biostudies-literature