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Formation of cobalt-oxygen intermediates by dioxygen activation at a mononuclear nonheme cobalt(ii) center

Title
Formation of cobalt-oxygen intermediates by dioxygen activation at a mononuclear nonheme cobalt(ii) center
Authors
Malik D.D.Chandra A.Seo M.S.Lee Y.-M.Farquhar E.R.Mebs S.Dau H.Ray K.Nam W.
Ewha Authors
남원우이용민
SCOPUS Author ID
남원우scopus; 이용민scopusscopus
Issue Date
2021
Journal Title
Dalton Transactions
ISSN
1477-9226JCR Link
Citation
Dalton Transactions vol. 50, no. 34, pp. 11889 - 11898
Publisher
Royal Society of Chemistry
Indexed
SCIE; SCOPUS WOS scopus
Document Type
Article
Abstract
A mononuclear nonheme cobalt(ii) complex, [(TMG3tren)CoII(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, [(TMG3tren)CoIV(O)]2+-(Sc(OTf)3)n(3), in >90% yield upon addition of a redox-inactive metal ion, Sc(OTf)3. Intermediates2and3represent the cobalt analogues of the proposed iron(ii)-alkylperoxide precursor that converts to an iron(iv)-oxo intermediateviaO-O bond heterolysis in pterin-dependent nonheme iron oxygenases. In reactivity studies,2shows an amphoteric reactivity in electrophilic and nucleophilic reactions, whereas3is 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. © The Royal Society of Chemistry 2021.
DOI
10.1039/d1dt01996a
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자연과학대학 > 화학·나노과학전공 > Journal papers
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