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:10.1021/jacs.2c00055

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

Abstract

Here, 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 anew 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-butenaloxide is identified based on computed an harmonic 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 10⁸s^-1at ca. 3000 cm^-1 in good accord with the experiment.more »« less

Authors:

^[1]; Qian, Yujie ^[1]; Sojdak, Christopher A. ^[1];

^[1];

^[2];

^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

Publication Date:: Mon Mar 28 00:00:00 EDT 2022

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); Independent Research Fund Denmark; National Institutes of Health (NIH); Carlsberg Foundation

OSTI Identifier:: 1879877

Grant/Contract Number:: AC02-06CH11357; CHE-1955068; ACI-1548562; CF18–0614; 9036–00016B; 1S10RR023444; 1S10RR022442; 3R01GM118510-03S1; 3R01GM087605-06S1; DGE-1845298

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 144; Journal Issue: 13; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Hansen, Anne S., Qian, Yujie, Sojdak, Christopher A., Kozlowski, Marisa C., Esposito, Vincent J., Francisco, Joseph S., Klippenstein, Stephen J., and Lester, Marsha I. Rapid Allylic 1,6 H-Atom Transfer in an Unsaturated Criegee Intermediate.  United States: N. p., 2022. 
Web.  doi:10.1021/jacs.2c00055.

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                    Hansen, Anne S., Qian, Yujie, Sojdak, Christopher A., Kozlowski, Marisa C., Esposito, Vincent J., Francisco, Joseph S., Klippenstein, Stephen J., & Lester, Marsha I. Rapid Allylic 1,6 H-Atom Transfer in an Unsaturated Criegee Intermediate.  United States.  https://doi.org/10.1021/jacs.2c00055

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                    Hansen, Anne S., Qian, Yujie, Sojdak, Christopher A., Kozlowski, Marisa C., Esposito, Vincent J., Francisco, Joseph S., Klippenstein, Stephen J., and Lester, Marsha I. Mon .  
"Rapid Allylic 1,6 H-Atom Transfer in an Unsaturated Criegee Intermediate".  United States.  https://doi.org/10.1021/jacs.2c00055.  https://www.osti.gov/servlets/purl/1879877.

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@article{osti_1879877,

  title        = {Rapid Allylic 1,6 H-Atom Transfer in an Unsaturated Criegee Intermediate},

  author       = {Hansen, Anne S. and Qian, Yujie and Sojdak, Christopher A. and Kozlowski, Marisa C. and Esposito, Vincent J. and Francisco, Joseph S. and Klippenstein, Stephen J. and Lester, Marsha I.},

  abstractNote = {Here, 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 anew 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-butenaloxide is identified based on computed an harmonic 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 keff(E) on the order of 108s-1at 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. 106s-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.},

  doi          = {10.1021/jacs.2c00055},

  journal      = {Journal of the American Chemical Society},

  number       = 13,

  volume       = 144,

  place        = {United States},

  year         = {Mon Mar 28 00:00:00 EDT 2022},

  month        = {Mon Mar 28 00:00:00 EDT 2022}

}

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