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CO Oxidation by Group 3 Metal Monoxide Cations Supported on [Fe(CO)4]2−.
- Source :
-
Angewandte Chemie . 11/6/2017, Vol. 129 Issue 45, p14284-14289. 6p. - Publication Year :
- 2017
-
Abstract
- Infrared photodissociation spectroscopy of mass-selected heteronuclear cluster anions in the form of OMFe(CO)5− (M=Sc, Y, La) indicates that all these anions involve an 18-electron [Fe(CO)4]2− building block that is bonded with the M center through two bridged carbonyl ligands. The OLaFe(CO)5− anion is determined to be a CO-tagged complex involving a [Fe(CO)4]2−[LaO]+ anion core. In contrast, the OYFe(CO)5− anion is characterized to have a [Fe(CO)4]2−[Y(η2-CO2)]+ structure involving a side-on bonded CO2 ligand. The CO-tagged complex and the [Fe(CO)4]2−[Sc(η2-CO2)]+ isomer co-exist for the OScFe(CO)5− anion. These observations indicate that both the ScO+ and YO+ cations supported on [Fe(CO)4]2− are able to oxidize CO to CO2. Theoretical analyses show that [Fe(CO)4]2− coordination significantly weakens the MO+ bond and decreases the energy gap of the interacting valence orbitals between MO+ and CO, leading to the CO oxidation reactions being both thermodynamically exothermic and kinetically facile. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00448249
- Volume :
- 129
- Issue :
- 45
- Database :
- Academic Search Index
- Journal :
- Angewandte Chemie
- Publication Type :
- Academic Journal
- Accession number :
- 125891328
- Full Text :
- https://doi.org/10.1002/ange.201707898