Journal article
Two Spin-State Reactivity in the Activation and Cleavage of CO2by [ReO2]-
V Canale, R Robinson, A Zavras, GN Khairallah, N d'Alessandro, BF Yates, RAJ O'Hair
Journal of Physical Chemistry Letters | AMER CHEMICAL SOC | Published : 2016
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 C-O bond. Isotope labeling experiments using [Re18O2]-reveal that18O/16O scrambling does not occur prior to cleavage of the C-O 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]-versus1[ReO3]-), both reaction surfaces were examined in detail and multiple [O2Re-CO2]-intermediates and transition structures were located and minimum energy crossing points were calc..
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Grants
Awarded by Australian Research Council
Funding Acknowledgements
We thank the ARC for financial support via the ARC Centre of Excellence for Free Radical Chemistry and Biotechnology (CE0561607), the award of an ARF to G.N.K (DP1096134), and Discovery Projects to B.F.Y. (DP120101937) and R.A.J.O. (DP150101388). We gratefully acknowledge the generous allocation of computing time from the Melbourne University high performance computing Facility (Edward), from the Tasmanian Partnership for Advanced Computing (Katabatic), and from the National Computing Infrastructure (Raijin). V.C. thanks the University G.d'Annunzio of Chieti-Pescara and the Italian Ministry of Education, University and Research for financial support (Fondo Sostegno Giovani). We thank Prof. Jonathon White for a gift of H<INF>2</INF><SUP>[18]</SUP>O and Prof. Helmut Schwarz for a preprint of ref 13.