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Formic acid catalyzed isomerization and adduct formation of an isoprene-derived Criegee intermediate: experiment and theory

Vansco, Michael F. and Caravan, Rebecca L. and Pandit, Shubhrangshu and Zuraski, Kristen and Winiberg, Frank A. F. and Au, Kendrew and Bhagde, Trisha and Trongsiriwat, Nisalak and Walsh, Patrick J. and Osborn, David L. and Percival, Carl J. and Klippenstein, Stephen J. and Taatjes, Craig A. and Lester, Marsha I. (2020) Formic acid catalyzed isomerization and adduct formation of an isoprene-derived Criegee intermediate: experiment and theory. Physical Chemistry Chemical Physics, 22 (46). pp. 26796-26805. ISSN 1463-9076. doi:10.1039/d0cp05018k.

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Isoprene is the most abundant non-methane hydrocarbon emitted into the Earth's atmosphere. Ozonolysis is an important atmospheric sink for isoprene, which generates reactive carbonyl oxide species (R₁R₂C O⁺O⁻) known as Criegee intermediates. This study focuses on characterizing the catalyzed isomerization and adduct formation pathways for the reaction between formic acid and methyl vinyl ketone oxide (MVK-oxide), a four-carbon unsaturated Criegee intermediate generated from isoprene ozonolysis. syn-MVK-oxide undergoes intramolecular 1,4 H-atom transfer to form a substituted vinyl hydroperoxide intermediate, 2-hydroperoxybuta-1,3-diene (HPBD), which subsequently decomposes to hydroxyl and vinoxylic radical products. Here, we report direct observation of HPBD generated by formic acid catalyzed isomerization of MVK-oxide under thermal conditions (298 K, 10 torr) using multiplexed photoionization mass spectrometry. The acid catalyzed isomerization of MVK-oxide proceeds by a double hydrogen-bonded interaction followed by a concerted H-atom transfer via submerged barriers to produce HPBD and regenerate formic acid. The analogous isomerization pathway catalyzed with deuterated formic acid (D2-formic acid) enables migration of a D atom to yield partially deuterated HPBD (DPBD), which is identified by its distinct mass (m/z 87) and photoionization threshold. In addition, bimolecular reaction of MVK-oxide with D2-formic acid forms a functionalized hydroperoxide adduct, which is the dominant product channel, and is compared to a previous bimolecular reaction study with normal formic acid. Complementary high-level theoretical calculations are performed to further investigate the reaction pathways and kinetics.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Vansco, Michael F.0000-0002-6189-6272
Caravan, Rebecca L.0000-0002-2936-7952
Pandit, Shubhrangshu0000-0002-2744-9006
Zuraski, Kristen0000-0003-3149-6611
Winiberg, Frank A. F.0000-0003-2801-5581
Bhagde, Trisha0000-0002-5673-7648
Trongsiriwat, Nisalak0000-0002-8582-1750
Walsh, Patrick J.0000-0001-8392-4150
Osborn, David L.0000-0003-4304-8218
Percival, Carl J.0000-0003-2525-160X
Klippenstein, Stephen J.0000-0001-6297-9187
Taatjes, Craig A.0000-0002-9271-0282
Lester, Marsha I.0000-0003-2367-3497
Additional Information:© 2020 the Owner Societies. Submitted 22 Sep 2020; Accepted 10 Nov 2020; First published 11 Nov 2020. This research was supported by the U.S. Department of Energy-Basic Energy Sciences under grant DE-FG02-87ER13792 (MIL). This material is also based upon work supported by the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences (BES), U.S. Department of Energy (USDOE). Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the USDOE's National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the USDOE or the United States Government. This material is based in part on research at Argonne supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences under Contract No. DE-AC02-06CH11357. The Advanced Light Source is supported by the Director, Office of Science, BES/USDOE under Contract DE-AC02-05CH11231 at Lawrence Berkeley National Laboratory. This research was carried out in part by the Jet Propulsion Laboratory, California Institute of Technology, under contract with the National Aeronautics and Space Administration (NASA), supported by the Upper Atmosphere Research and Tropospheric Chemistry program. The contributions of RLC and KZ were in part supported by appointments to the NASA Postdoctoral Program at the NASA Jet Propulsion Laboratory, administered by Universities Space Research Association under contract with NASA. PJW thanks the NSF (CHE-1902509). California Institute of Technology. © 2020. All rights reserved. We are grateful to Dr. Leonid Sheps (Sandia) and Dr. Ahren Jasper (Argonne) for useful discussions. Conflicts of interest: There are no conflicts to declare.
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG02-87ER13792
Department of Energy (DOE)DE-NA0003525
Department of Energy (DOE)DE-AC02-06CH11357
Department of Energy (DOE)DE-AC02-05CH11231
NASA Postdoctoral ProgramUNSPECIFIED
Issue or Number:46
Record Number:CaltechAUTHORS:20201123-082531900
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Official Citation:Formic acid catalyzed isomerization and adduct formation of an isoprene-derived Criegee intermediate: experiment and theory. Phys. Chem. Chem. Phys., 2020, 22, 26796-26805; DOI: 10.1039/d0cp05018k
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:106776
Deposited By: Tony Diaz
Deposited On:23 Nov 2020 16:38
Last Modified:16 Nov 2021 18:56

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