Functionalized Hydroperoxide Formation from the Reaction of Methacrolein-Oxide, an Isoprene-Derived Criegee Intermediate, with Formic Acid: Experiment and Theory

Creators: Vansco, Michael F.; Zuraski, Kristen; Winiberg, Frank A. F.; Au, Kendrew; Trongsiriwat, Nisalak; Walsh, Patrick J.; Osborn, David L.; Percival, Carl J.; Klippenstein, Stephen J.; Taatjes, Craig A.; Lester, Marsha I.; Caravan, Rebecca L.

Abstract

Methacrolein oxide (MACR-oxide) is a four-carbon, resonance-stabilized Criegee intermediate produced from isoprene ozonolysis, yet its reactivity is not well understood. This study identifies the functionalized hydroperoxide species, 1-hydroperoxy-2-methylallyl formate (HPMAF), generated from the reaction of MACR-oxide with formic acid using multiplexed photoionization mass spectrometry (MPIMS, 298 K = 25 °C, 10 torr = 13.3 hPa). Electronic structure calculations indicate the reaction proceeds via an energetically favorable 1,4-addition mechanism. The formation of HPMAF is observed by the rapid appearance of a fragment ion at m/z 99, consistent with the proposed mechanism and characteristic loss of HO₂ upon photoionization of functional hydroperoxides. The identification of HPMAF is confirmed by comparison of the appearance energy of the fragment ion with theoretical predictions of its photoionization threshold. The results are compared to analogous studies on the reaction of formic acid with methyl vinyl ketone oxide (MVK-oxide), the other four-carbon Criegee intermediate in isoprene ozonolysis.

Additional Information

© 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). Received: 22 April 2021 / Revised: 11 May 2021 / Accepted: 13 May 2021 / Published: 20 May 2021. (This article belongs to the Special Issue Experimental and Computational Studies of Oxidation Reactions in Atmospheric and Combustion Chemistry). 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). Author Contributions. Conceptualization, M.F.V., S.J.K., C.A.T., C.J.P., M.I.L., and R.L.C.; formal analysis, M.F.V. and R.L.C.; funding acquisition, K.Z., P.J.W., D.L.O., C.J.P., S.J.K., C.A.T., M.I.L., and R.L.C.; investigation, M.F.V., K.Z., F.A.F.W., K.A., C.J.P., C.A.T., M.I.L., and R.L.C.; methodology, N.T., P.J.W., D.L.O., S.J.K., and C.A.T.; project administration, M.F.V., P.J.W., D.L.O., C.J.P., S.J.K., C.A.T., M.I.L., and R.L.C.; resources, N.T., P.J.W., D.L.O., C.J.P., C.A.T., and M.I.L.; software, D.L.O., C.A.T., and S.J.K.; supervision, M.F.V., P.J.W., D.L.O., C.J.P., S.J.K., C.A.T., M.I.L., and R.L.C.; validation, M.F.V., S.J.K., and R.L.C.; visualization, M.F.V. and R.L.C.; writing—original draft, M.F.V., S.J.K., C.A.T., M.I.L., and R.L.C.; writing—review & editing, M.F.V., K.Z., F.A.F.W., K.A., P.J.W., D.L.O., C.J.P., S.J.K., C.A.T., M.I.L., and R.L.C. All authors have read and agreed to the published version of the manuscript. Supplementary Materials. The following are available online, additional experimental details, computed stationary point geometries, and energy corrections. Section S1. HCO₂-loss fragment ion, Section S2. Theoretical reaction pathways, Section S3. Stationary point geometries, Table S1. Stationary point energies and corrections, Figure S1 Temporal profile of m/z 87 as a function of formic acid concentration, Figure S2: Comparison of m/z 87 and 99 integrated signals as a function of formic acid concentration, Figure S3: Photoionization spectrum of m/z 87 with and without formic acid added, Figure S4. Reaction coordinate for the 1,4-addition of syn-cis-MACR-oxide with formic acid, Figure S5. Reaction coordinate for the 1,4-addition of syn-trans-MACR-oxide with formic acid, Figure S6. Reaction coordinate for the spectator catalysis of syn-cis-MACR-oxide to dioxole. Institutional Review Board Statement. Not applicable. Informed Consent Statement. Not applicable. Data Availability Statement. All data is available in the main text, in the supplementary materials, or on reasonable request. The authors declare no conflict of interest. Sample Availability. Samples of the compounds are not available from the authors.

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