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Two Spin-State Reactivity in the Activation and Cleavage of CO2 by [ReO2]-
journal contribution
posted on 2023-05-19, 02:48 authored by Canale, V, Robinson Jr, R, Zavras, A, Khairallah, GN, d'Alessandro, N, Brian YatesBrian Yates, O'Hair, RAJThe 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 that 18O/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]− 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(η2–C,O–CO2)]– species most likely initiates C–O bond activation and cleavage. The stronger binding affinity of CO2 within this species and the greater instabilities of other [O2Re–CO2)]– intermediates are significant enough that oxygen atom exchange is avoided.
Funding
Australian Research Council
History
Publication title
Journal of Physical Chemistry LettersVolume
7Issue
10Pagination
1934-1938ISSN
1948-7185Department/School
School of Natural SciencesPublisher
American Chemical SocietyPlace of publication
United StatesRights statement
Copyright 2016 American Chemical SocietyRepository Status
- Restricted