M-O Bonding Beyond the Oxo Wall: Spectroscopy and Reactivity of Cobalt(III)-Oxyl and Cobalt(III)-Oxo Complexes.

ABSTRACT: 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)Co^III (O)]⁺ (1) and [(N4Py)Co^IV (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 c

SUBMITTER: Andris E 

PROVIDER: S-EPMC6618258 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature