Rapid allylic 1,6 H-atom transfer in an unsaturated Criegee intermediate

Hansen, Anne S.; Qian, Yujie; Sojdak, Christopher A.; Kozlowski, Marisa C.; Esposito, Vincent J.; Francisco, Joseph S.; Klippenstein, Stephen J.; Lester, Marsha I.

doi:10.5281/zenodo.6323758

2021

DOI: 10.5281/zenodo.6323758

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Rapid allylic 1,6 H-atom transfer in an unsaturated Criegee intermediate

Anne S. Hansen

Yujie Qian

Christopher A. Sojdak

et al.

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“…The data that support the findings of this study are available within the article and its supporting information. In addition, the MESS input files and optimized geometries are provided in Zenodo (ref ), while other supplementary information is presented in the Corrigendum (ref ).…”

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Rapid Allylic 1,6 H-Atom Transfer in an Unsaturated Criegee Intermediate

et al. 2022

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A novel allylic 1,6 hydrogen-atom-transfer mechanism is established through infrared activation of the 2-butenal oxide Criegee intermediate, resulting in very rapid unimolecular decay to hydroxyl (OH) radical products. A new precursor, Z/E-1,3-diiodobut-1-ene, is synthesized and photolyzed in the presence of oxygen to generate a new four-carbon Criegee intermediate with extended conjugation across the vinyl and carbonyl oxide groups that facilitates rapid allylic 1,6 H-atom transfer. A low-energy reaction pathway involving isomerization of 2-butenal oxide from a lower-energy (tZZ) conformer to a higher-energy (cZZ) conformer followed by 1,6 hydrogen transfer via a seven-membered ring transition state is predicted theoretically and shown experimentally to yield OH products. The low-lying (tZZ) conformer of 2-butenal oxide is identified based on computed anharmonic frequencies and intensities of its conformers. Experimental IR action spectra recorded in the fundamental CH stretch region with OH product detection by UV laser-induced fluorescence reveal a distinctive IR transition of the low-lying (tZZ) conformer at 2996 cm–1 that results in rapid unimolecular decay to OH products. Statistical RRKM calculations involving a combination of conformational isomerization and unimolecular decay via 1,6 H-transfer yield an effective decay rate k eff(E) on the order of 108 s–1 at ca. 3000 cm–1 in good accord with the experiment. Unimolecular decay proceeds with significant enhancement due to quantum mechanical tunneling. A rapid thermal decay rate of ca. 106 s–1 is predicted by master-equation modeling of 2-butenal oxide at 298 K, 1 bar. This novel unimolecular decay pathway is expected to increase the nonphotolytic production of OH radicals upon alkene ozonolysis in the troposphere.

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Rapid Allylic 1,6 H-Atom Transfer in an Unsaturated Criegee Intermediate

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Rapid allylic 1,6 H-atom transfer in an unsaturated Criegee intermediate

Cited by 1 publication

References 0 publications

Rapid Allylic 1,6 H-Atom Transfer in an Unsaturated Criegee Intermediate

Rapid Allylic 1,6 H-Atom Transfer in an Unsaturated Criegee Intermediate

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