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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, RAJ
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 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 Letters

Volume

7

Issue

10

Pagination

1934-1938

ISSN

1948-7185

Department/School

School of Natural Sciences

Publisher

American Chemical Society

Place of publication

United States

Rights statement

Copyright 2016 American Chemical Society

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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