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Issue 28, 2017
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A combined theoretical and experimental study on the mechanism of spiro-adamantyl-1,2-dioxetanone decomposition

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Abstract

1,2-Dioxetanones have been considered as model compounds for bioluminescence processes. The unimolecular decomposition of these prototypes leads mainly to the formation of triplet excited states whereas in the catalysed decomposition of these peroxides singlet states are formed preferentially. Notwithstanding, these cyclic peroxides are important models to understand the general principles of chemiexcitation as they can be synthesised, purified and characterised. We report here results of experimental and theoretical approaches to investigating the decomposition mechanism of spiro-adamantyl-1,2-dioxetanone. The activation parameters in the unimolecular decomposition of this derivative have been determined by isothermal kinetic measurements (30–70 °C) and the chemiluminescence activation energy calculated from the correlation of emission intensities. The activation energy for peroxide decomposition proved to be considerably lower than the chemiluminescence activation energy indicating the existence of different reaction pathways for ground and excited state formation. These experimental results are compared with the calculations at the complete active space second-order perturbation theory (CASPT2), which reveal a two-step biradical mechanism starting by weak peroxide bond breakage followed by carbon–carbon elongation. The theoretical findings also indicate different transition state energies on the excited and ground state surfaces during the C–C bond cleavage in agreement with the experimental activation parameters.

Graphical abstract: A combined theoretical and experimental study on the mechanism of spiro-adamantyl-1,2-dioxetanone decomposition

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Publication details

The article was received on 09 Nov 2016, accepted on 09 Mar 2017 and first published on 20 Mar 2017


Article type: Paper
DOI: 10.1039/C6RA26575H
Citation: RSC Adv., 2017,7, 17462-17472
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    A combined theoretical and experimental study on the mechanism of spiro-adamantyl-1,2-dioxetanone decomposition

    P. Farahani, M. A. Oliveira, I. Fdez. Galván and W. J. Baader, RSC Adv., 2017, 7, 17462
    DOI: 10.1039/C6RA26575H

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