Abstract
Abstract Some specific picket fence porphyrinatocobalt(II) complexes were newly synthesized and characterized. The complexes contain one protic substituent capable of forming intramolecular hydrogen bond with the dioxygen molecule coordinated to the central metal ion. Their reactions with dioxygen molecule were measured spectrometrically in solution containing an axial base, and the thermodynamic functions were determined. The results indicate that the protic groups promote the irreversible oxidation of Co(II) to Co(III). This effect may be ascribed to decreased electron density at the central Co(II) ion, which is resulted from shifted electron density toward the hydrogen atom of the protic group through the coordinated O2 molecule by hydrogenbond formation or the like. It is also found that the complexes prepared have lower O2 affinity than the corresponding complexes with no protic substituent and that the decreased binding energy −ΔH° of the dioxygen molecule to the complexes brings about the increased...
Published Version
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