Radical Behavior of CO2 versus its Deoxygenation Promoted by Vanadium Aryloxide Complexes: How the Geometry of Intermediate CO2 -Adducts Determines the Reactivity

Camilo J Viasus; Nicholas P Alderman; Sebastiano Licciulli; Ilia Korobkov; Sandro Gambarotta

doi:10.1002/chem.201702943

Radical Behavior of CO₂ versus its Deoxygenation Promoted by Vanadium Aryloxide Complexes: How the Geometry of Intermediate CO₂ -Adducts Determines the Reactivity

Chemistry. 2017 Dec 6;23(68):17269-17278. doi: 10.1002/chem.201702943. Epub 2017 Nov 14.

Authors

Camilo J Viasus¹, Nicholas P Alderman¹, Sebastiano Licciulli¹, Ilia Korobkov¹, Sandro Gambarotta¹

Affiliation

¹ Department of Chemistry and Biomolecular Science, University of Ottawa, 10 Marie Curie, Ottawa, ON, Canada.

PMID: 29030892
DOI: 10.1002/chem.201702943

Abstract

The reactivity of carbon dioxide with vanadium(III) aryloxo complexes has been investigated. The formation of either carbon monoxide or incorporation into the ligand system with the ultimate formation of organic ester was observed depending on the overall electron donor ability of the ligand field. DFT calculations were carried out to investigate the proposed mechanism for carbon dioxide coordination and reduction.

Keywords: carbon dioxide; carbon monoxide; density functional calculations; deoxygenation; vanadium.