Journal of the American Chemical Society p. 2273 - 2278 (1990)
Update date:2022-08-11
Topics:
Bakac, Andreja
Espenson, James H.
The macrocyclic cobalt(II) complex (H2O)nCo(C-meso-Me6[14]aneN4) 2+ (L2Co2+) binds oxygen to yield L2CoO22+. The rate constants for the binding and release of O2 in aqueous solutions at 25°C have values 5.0 × 106 M-1 s-1 and 1.66 × 104 s-1, respectively. There is no evidence for the formation of a binuclear μ-peroxo complex. The ESR parameters of the oxygen adduct in toluene at 120 K, g∥ = 2.108, g⊥ = 1.96, A∥, = 3.81 × 10-3 cm-1, A⊥ = 2.94 × 10-3 cm-1, are consistent with the formulation of the complex as a 1:1 adduct with the unpaired spin density residing on the oxygen. The laser flash photolysis of L2CoO22+ (λirr 490 nm) induces the cleavage of the cobalt-oxygen bond, L2CoO22+ →hv L2Co2+ + O2.
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