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Two Spin-State Reactivity in the Activation and Cleavage of CO2 by [ReO2]-

Citation

Canale, V and Robinson Jr, R and Zavras, A and Khairallah, GN and d'Alessandro, N and Yates, BF and O'Hair, RAJ, Two Spin-State Reactivity in the Activation and Cleavage of CO2 by [ReO2]-, Journal of Physical Chemistry Letters, 7, (10) pp. 1934-1938. ISSN 1948-7185 (2016) [Refereed Article]

Copyright Statement

Copyright 2016 American Chemical Society

DOI: doi:10.1021/acs.jpclett.6b00754

Abstract

The rhenium dioxide anion [ReO2] reacts with carbon dioxide in a linear ion trap mass spectrometer to produce [ReO3] corresponding to activation and cleavage of a CO bond. Isotope labeling experiments using [Re18O2] reveal that 18O/16O scrambling does not occur prior to cleavage of the CO bond. Density functional theory calculations were performed to examine the mechanism for this oxygen atom abstraction reaction. Because the spins of the ground states are different for the reactant and product ions (3[ReO2] versus 1[ReO3]), both reaction surfaces were examined in detail and multiple [O2Re-CO2] intermediates and transition structures were located and minimum energy crossing points were calculated. The computational results show that the intermediate [O2Re(η2C,OCO2)] species most likely initiates CO bond activation and cleavage. The stronger binding affinity of CO2 within this species and the greater instabilities of other [O2ReCO2)] intermediates are significant enough that oxygen atom exchange is avoided.

Item Details

Item Type:Refereed Article
Keywords:carbon dioxide
Research Division:Chemical Sciences
Research Group:Physical Chemistry (incl. Structural)
Research Field:Catalysis and Mechanisms of Reactions
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Robinson Jr, R (Dr Robert Robinson)
Author:Yates, BF (Professor Brian Yates)
ID Code:114970
Year Published:2016
Funding Support:Australian Research Council (DP120101937)
Web of Science® Times Cited:1
Deposited By:Chemistry
Deposited On:2017-03-03
Last Modified:2017-04-05
Downloads:0

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