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Formation of cobalt–oxygen intermediates by dioxygen activation at a mononuclear nonheme cobalt(<scp>ii</scp>) center

Deesha D. Malik, Anirban Chandra, Mi Sook Seo, Yong‐Min Lee, Erik R. Farquhar, Stefan Mebs, Holger Dau, Kallol Ray, Wonwoo Nam

2021Dalton Transactions21 citationsDOIOpen Access PDF

Abstract

. Intermediates 2 and 3 represent the cobalt analogues of the proposed iron(ii)-alkylperoxide precursor that converts to an iron(iv)-oxo intermediate via O-O bond heterolysis in pterin-dependent nonheme iron oxygenases. In reactivity studies, 2 shows an amphoteric reactivity in electrophilic and nucleophilic reactions, whereas 3 is an electrophilic oxidant. To the best of our knowledge, the present study reports the first example showing the generation of cobalt-oxygen intermediates by activating dioxygen at a cobalt(ii) center and the reactivities of the cobalt-oxygen intermediates in oxidation reaction.

Topics & Concepts

CobaltChemistryHeterolysisReactivity (psychology)Medicinal chemistryElectrophilePhotochemistryNucleophileRedoxCatalysisInorganic chemistryOrganic chemistryMedicineAlternative medicinePathologyMetal-Catalyzed Oxygenation MechanismsPorphyrin and Phthalocyanine ChemistryMetal complexes synthesis and properties
Formation of cobalt–oxygen intermediates by dioxygen activation at a mononuclear nonheme cobalt(<scp>ii</scp>) center | Litcius