Carbonate formation from CO2 via oxo versus oxalate pathway: Theoretical investigations into the mechanism of uranium-mediated carbonate formation

Castro L, Lam OP, Bart SC, Meyer K, Maron L (2010)

Publication Type: Journal article, Original article

Publication year: 2010

Journal

Organometallics American Chemical Society

Original Authors: Castro L., Lam O.P., Bart S.C., Meyer K., Maron L.

Publisher: American Chemical Society

Book Volume: 29

Pages Range: 5504-5510

Journal Issue: 21

DOI: 10.1021/om100479r

Abstract

We report theoretical investigations of the reaction of [(( ArO)mes)U] with CO in order to support previously reported experimental data. Experimentally, the reaction in toluene leads to the immediate formation of the bridging carbonate complex [{(( ArO)mes)U}(μ- η:η-CO)] at room temperature. DFT calculations show that the preferred reaction pathway is a three-step mechanism: first, the formation of a dinuclear CO complex, followed by concomitant release of CO, forming the corresponding bridging μ-oxo species. The final step involves insertion of a CO molecule into a U-O bond, forming the carbonate product. Calculations reveal this three-step process to be thermodynamically favorable and kinetically accessible. An alternate pathway that proceeds through an oxalate dinuclear complex is also explored. Although the oxalate complex is calculated to be the thermodynamic product of the reaction, a high activation barrier prevents its formation. © 2010 American Chemical Society.

Authors with CRIS profile

Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Université Fédérale de Toulouse Midi-Pyrénées FR France (FR)

How to cite

APA:

Castro, L., Lam, O.P., Bart, S.C., Meyer, K., & Maron, L. (2010). Carbonate formation from CO2 via oxo versus oxalate pathway: Theoretical investigations into the mechanism of uranium-mediated carbonate formation. Organometallics, 29(21), 5504-5510. https://doi.org/10.1021/om100479r

MLA:

Castro, Ludovic, et al. "Carbonate formation from CO2 via oxo versus oxalate pathway: Theoretical investigations into the mechanism of uranium-mediated carbonate formation." Organometallics 29.21 (2010): 5504-5510.

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