A Highly Reactive Co(μ-O) Diamond Core Complex that Cleaves C-H Bonds.
Summary of "A Highly Reactive Co(μ-O) Diamond Core Complex that Cleaves C-H Bonds."
The selective activation of strong sp C-H bonds at mild conditions is a key step in many biological and synthetic transformations, and an unsolved challenge for synthetic chemists. In nature, soluble methane monooxygenase (sMMO) is one representative example of nonheme dinuclear iron-dependent enzymes that activate strong sp C-H bonds by a high-valent diiron(IV) intermediate . To date, synthetic model complexes of sMMO- have shown limited abilities to oxidize strong C-H bonds. In this work, we generated a high-valent Co(μ-O) complex supported by a tetradentate TPA ligand via one-electron oxidation of its Co(μ-O) precursor . Characterization of and using X-ray absorption spectroscopy and DFT calculations showed that both species possess a diamond core structure with a short Co•••Co distance of 2.78 Å. Furthermore, is an EPR active species showing an = 1/2 signal with clear hyperfine splittings originated from the coupling of the Co nuclear spin with the electronic spin. Importantly, is a highly reactive oxidant for sp C-H bonds, and an oxygenation reagent. has the highest rate constant (1.5 M s at -60 C) for oxidizing 9,10-dihydroanthracene (DHA) compared to diamond core complexes of other first-row transition metals including Mn, Fe and Cu reported previously. Specifically, is about 4-5 orders of magnitude more reactive than the diiron analogs Fe(μ-O) and Fe(μ-O) supported by TPA and related ligands. These findings shed light on future development of more reactive approaches for C-H bond activation by bio-inspired dicobalt complexes.
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Journal Details
This article was published in the following journal.
Name: Journal of the American Chemical Society
ISSN: 1520-5126
Pages:
Links
- PubMed Source: http://www.ncbi.nlm.nih.gov/pubmed/31794198
- DOI: http://dx.doi.org/10.1021/jacs.9b09531
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