Terminal oxo complexes of late transition metals are frequently proposed reactive intermediates. However, they are scarcely known beyond Group 8. Using mass spectrometry, we prepared and characterized two such complexes: [(N4Py)CoIII (O)]+ (1) and [(N4Py)CoIV (O)]2+ (2). Infrared photodissociation spectroscopy revealed that the Co-O bond in 1 is rather strong, in accordance with its lack of chemical reactivity. On the contrary, 2 has a very weak Co-O bond characterized by a stretching frequency of ≤659 cm-1 . Accordingly, 2 can abstract hydrogen atoms from non-activated secondary alkanes. Previously, this reactivity has only been observed in the gas phase for small, coordinatively unsaturated metal complexes. Multireference ab-initio calculations suggest that 2, formally a cobalt(IV)-oxo complex, is best described as cobalt(III)-oxyl. Our results provide important data on changes to metal-oxo bonding behind the oxo wall and show that cobalt-oxo complexes are promising targets for developing highly active C-H oxidation catalysts.

Departament de Quimica and Institute of Computational Chemistry and Catalysis University of Girona Campus Montilivi Girona 17071 Spain

Department of Organic Chemistry Faculty of Science Charles University Hlavova 2030 8 128 43 Prague 2 Czech Republic

J Heyrovsky Institute of Physical Chemistry of the CAS v v i Dolejškova 2155 3 1822 3 Prague 8 Czech Republic

Radboud University Nijmegen Institute for Molecules and Materials Heyendaalseweg 135 6525 AJ Nijmegen The Netherlands

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