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A combined theoretical and experimental study onthe mechanism of spiro-adamantyl-1,2-dioxetanone decomposition
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-8453-5664
2017 (English)In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 7, p. 17462-17472Article in journal (Refereed) Published
Abstract [en]

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

Place, publisher, year, edition, pages
2017. Vol. 7, p. 17462-17472
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Organic Chemistry
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URN: urn:nbn:se:kth:diva-215157DOI: 10.1039/c6ra26575hOAI: oai:DiVA.org:kth-215157DiVA, id: diva2:1146681
Note

QC 20171004

Available from: 2017-10-03 Created: 2017-10-03 Last updated: 2017-11-29Bibliographically approved

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Farahani, Pooria

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