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Activation of Molecular Oxygen by a Cobalt(II) Tetra-NHC Complex*.


ABSTRACT: The first dicobalt(III) ?2 -peroxo N-heterocyclic carbene (NHC) complex is reported. It can be quantitatively generated from a cobalt(II) compound bearing a 16-membered macrocyclic tetra-NHC ligand via facile activation of dioxygen from air at ambient conditions. The reaction proceeds via an end-on superoxo intermediate as demonstrated by EPR studies and DFT. The peroxo moiety can be cleaved upon addition of acetic acid, yielding the corresponding CoIII acetate complex going along with H2 O2 formation. In contrast, both CoII and CoIII complexes are also studied as catalysts to utilize air for olefin and alkane oxidation reactions; however, not resulting in product formation. The observations are rationalized by DFT-calculations, suggesting a nucleophilic nature of the dicobalt(III) ?2 -peroxo complex. All isolated compounds are characterized by NMR, ESI-MS, elemental analysis, EPR and SC-XRD.

SUBMITTER: Schlagintweit JF 

PROVIDER: S-EPMC7898330 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

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Activation of Molecular Oxygen by a Cobalt(II) Tetra-NHC Complex*.

Schlagintweit Jonas F JF   Altmann Philipp J PJ   Böth Alexander D AD   Hofmann Benjamin J BJ   Jandl Christian C   Kaußler Clemens C   Nguyen Linda L   Reich Robert M RM   Pöthig Alexander A   Kühn Fritz E FE  

Chemistry (Weinheim an der Bergstrasse, Germany) 20201210 4


The first dicobalt(III) μ<sub>2</sub> -peroxo N-heterocyclic carbene (NHC) complex is reported. It can be quantitatively generated from a cobalt(II) compound bearing a 16-membered macrocyclic tetra-NHC ligand via facile activation of dioxygen from air at ambient conditions. The reaction proceeds via an end-on superoxo intermediate as demonstrated by EPR studies and DFT. The peroxo moiety can be cleaved upon addition of acetic acid, yielding the corresponding Co<sup>III</sup> acetate complex goin  ...[more]

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