Formation of cobalt–oxygen intermediates by dioxygen activation at a mononuclear nonheme cobalt(II) center.
In: Dalton Transactions: An International Journal of Inorganic Chemistry, Jg. 50 (2021-09-14), Heft 34, S. 11889-11898
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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. [ABSTRACT FROM AUTHOR]
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Titel: |
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 Transactions: An International Journal of Inorganic Chemistry, Jg. 50 (2021-09-14), Heft 34, S. 11889-11898 |
Veröffentlichung: | 2021 |
Medientyp: | academicJournal |
ISSN: | 1477-9226 (print) |
DOI: | 10.1039/d1dt01996a |
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