期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 28, 页码 9619-9624出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201904546
关键词
C-H activation; cobalt-oxo complexes; helium tagging; ion spectroscopy; iron-oxo complexes; oxo wall
资金
- European Research Council (ERC CoG) [682275]
- Czech Ministry of Education, Youth and Sports [LTAUSA17026]
- COST action ECOSTBio
- MINECO of Spain [CTQ2015-70795-P]
- Catalan DIUE of the Generalitat de Catalunya [2017SGR01378]
- Grant Agency of the Czech Republic [18-13093S]
Terminal oxo complexes of late transition metals are frequently proposed reactive intermediates. However, they are scarcely known beyond Group8. 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 <= 659cm(-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.
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