Formation of cobalt-oxygen intermediates by dioxygen activation at a mononuclear nonheme cobalt(II) center
In: Dalton Trans, 2021
academicJournal
Zugriff:
A mononuclear nonheme cobalt(II) complex, [(TMG(3)tren)Co(II)(OTf)](OTf) (1), activates dioxygen in the presence of hydrogen atom donor substrates, such as tetrahydrofuran and cyclohexene, resulting in the generation of a cobalt(II)-alkylperoxide intermediate (2), which then converts to the previously reported cobalt(IV)-oxo complex, [(TMG(3)tren)Co(IV)(O)](2+)-(Sc(OTf)(3))(n)] (3), in >90% yield upon addition of a redox-inactive metal ion, Sc(OTf)(3). 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.
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Formation of cobalt-oxygen intermediates by dioxygen activation at a mononuclear nonheme cobalt(II) center
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Autor/in / Beteiligte Person: | Malik, Deesha D. ; Chandra, Anirban ; Seo, Mi Sook ; Lee, Yong-Min ; Farquhar, Erik R. ; Mebs, Stefan ; Dau, Holger ; Ray, Kallol ; Nam, Wonwoo |
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Zeitschrift: | Dalton Trans, 2021 |
Veröffentlichung: | 2021 |
Medientyp: | academicJournal |
DOI: | 10.1039/d1dt01996a |
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