10.1021/jacs.8b06010.s001 Victoria P. Barber Victoria P. Barber Shubhrangshu Pandit Shubhrangshu Pandit Amy M. Green Amy M. Green Nisalak Trongsiriwat Nisalak Trongsiriwat Patrick J. Walsh Patrick J. Walsh Stephen J. Klippenstein Stephen J. Klippenstein Marsha I. Lester Marsha I. Lester Four-Carbon Criegee Intermediate from Isoprene Ozonolysis: Methyl Vinyl Ketone Oxide Synthesis, Infrared Spectrum, and OH Production American Chemical Society 2018 Criegee intermediates control RR unimolecular decay pathways OO OH products unimolecular decay rate master equation modeling yields Methyl Vinyl Ketone Oxide Synthesis IR absorption spectra CH Four-Carbon Criegee Intermediate carbonyl oxide species MACR-OO hydrogen atom transfer mechanism MVK-OO 2018-08-03 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Four-Carbon_Criegee_Intermediate_from_Isoprene_Ozonolysis_Methyl_Vinyl_Ketone_Oxide_Synthesis_Infrared_Spectrum_and_OH_Production/6985247 The reaction of ozone with isoprene, one of the most abundant volatile organic compounds in the atmosphere, produces three distinct carbonyl oxide species (RR′COO) known as Criegee intermediates: formaldehyde oxide (CH<sub>2</sub>OO), methyl vinyl ketone oxide (MVK-OO), and methacrolein oxide (MACR-OO). The nature of the substituents (R,R′ = H, CH<sub>3</sub>, CHCH<sub>2</sub>) and conformations of the Criegee intermediates control their subsequent chemistry in the atmosphere. In particular, unimolecular decay of MVK-OO is predicted to be the major source of hydroxyl radicals (OH) in isoprene ozonolysis. This study reports the initial laboratory synthesis and direct detection of MVK-OO through reaction of a photolytically generated, resonance-stabilized mono­iodo­alkene radical with O<sub>2</sub>. MVK-OO is characterized utilizing infrared (IR) action spectroscopy, in which IR activation of MVK-OO with two quanta of CH stretch at ca. 6000 cm<sup>–1</sup> is coupled with ultraviolet detection of the resultant OH products. MVK-OO is identified by comparison of the experimentally observed IR spectral features with theoretically predicted IR absorption spectra. For <i>syn</i>-MVK-OO, the rate of appearance of OH products agrees with the unimolecular decay rate predicted using statistical theory with tunneling. This validates the hydrogen atom transfer mechanism and computed transition-state barrier (18.0 kcal mol<sup>–1</sup>) leading to OH products. Theoretical calculations reveal an additional roaming pathway between the separating radical fragments, which results in other products. Master equation modeling yields a thermal unimolecular decay rate for <i>syn</i>-MVK-OO of 33 s<sup>–1</sup> (298 K, 1 atm). For <i>anti</i>-MVK-OO, theoretical exploration of several unimolecular decay pathways predicts that isomerization to dioxole is the most likely initial step to products.