Reaction of CO2 with a Vanadium(II) Aryl Oxide: Synergistic Activation of CO2/Oxo Groups towards H‐Atom Radical Abstraction |
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| Authors: | Camilo J. Viasus Dr. Nicholas P. Alderman Dr. Bulat Gabidullin Prof. Dr. Sandro Gambarotta |
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| Affiliation: | Department of Chemistry and Biomolecular Science, University of Ottawa, Ottawa, ON, Canada |
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| Abstract: | Treatment of divalent (ONNO)V(TMEDA) ( 1 ; ONNO=[2,4‐Me2‐2‐(OH)C6H2CH2]2N(CH2)2NMe2) with CO2 afforded [(ONNO)V]2(μ‐OH)(μ‐formate) ( 2 ). Whereas the bridging hydroxo and formate groups both originated from CO2, the H atoms present on the two residues were obtained through H‐atom radical abstraction from the solvent. DFT calculations revealed an initially linear CO2 bonding mode, followed by deoxygenation, and highlighted a synergistic effect between the so‐formed oxo group and an additional bridging CO2 residue in promoting radical behavior. |
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| Keywords: | carbon dioxide reduction density functional calculations hydrogen-atom abstraction radical reactions vanadium |
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