Abstract
The reactivity of cobalt(II) complexes toward dioxygen has long been recognized. Synthetic oxygen carriers reversibly form mononuclear superoxo and dinuclear μ-peroxo complexes. The bound O2 can be removed by pumping or flushing with an inert gas and this cycle can be repeated many times over. However, there is always some loss of reversibility, leading to cobalt- or ligand-centered oxidation. Dioxygen complexes are generally regarded as the source of activity in cobalt-catalyzed oxidations. The term dioxygen activation is used to describe the oxidation of added oxidizable substances via interaction with intermediate dioxygen complexes or their conversion products. Observations of this behavior have prompted extensive research into the vast area of homogeneous catalytic oxidation using cobalt complexes. In this review the progress made in the study of various cobalt-based catalyst systems in the last decade is surveyed. Catalytic oxidations by different classes of cobalt(II) complexes with salen, porphyrin, phthalocyanin, dioxime, amine, pyridine, cyclidene, peptide and carboxylato ligands are discussed with specific reference to the products formed and the underlying reaction mechanisms. For each catalyst type the oxidation of various substrates is reviewed, including substituted phenols, lignin phenolics, catechols, anilines, thiols, alcohols, diols, and alkenes. Oxygen insertions, NO oxidation and oxidations via alkylperoxo complexes are treated. Obviously due to the paramagnetic nature of cobalt(II) complexes, free-radical mechanisms are predominant in cobalt-catalyzed oxidations, permitting insight into the nature of reaction intermediates by the ESR technique.
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Simándi, L.I. (2003). Catalytic oxidations using cobalt(II) complexes. In: Simándi, L.I. (eds) Advances in Catalytic Activation of Dioxygen by Metal Complexes. Catalysis by Metal Complexes, vol 26. Springer, Boston, MA. https://doi.org/10.1007/0-306-47816-1_6
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DOI: https://doi.org/10.1007/0-306-47816-1_6
Publisher Name: Springer, Boston, MA
Print ISBN: 978-1-4020-1074-3
Online ISBN: 978-0-306-47816-1
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