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Synthesis, electronic spectroscopy and photochemistry of methacrolein oxide: A four carbon unsaturated Criegee intermediate from isoprene ozonolysis.

著者 Vansco MF , Marchetti B , Trongsiriwat N , Bhagde T , Wang G , Walsh PJ , Klippenstein SJ , Lester MI
J Am Chem Soc.2019 Aug 26 ; ():.
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Ozonolysis of isoprene, one of the most abundant volatile organic compounds in the Earth's atmosphere, generates the four-carbon unsaturated methacrolein oxide (MACR-oxide) Criegee intermediate. The first laboratory synthesis and direct detection of MACR-oxide is achieved through reaction of photolytically generated, resonance-stabilized iodoalkene radicals with oxygen. MACR-oxide is characterized on its first π*←π electronic transition using a ground state depletion method. MACR-oxide exhibits a broad UV-visible spectrum peaked at 380 nm with weak oscillatory structure at long wavelengths ascribed to vibrational resonances. Complementary theory predicts two strong π*←π transitions arising from extended conjugation across MACR-oxide with overlapping contributions from its four conformers. Electronic promotion to the 1ππ* state agrees well with experiment, and results in nonadiabatic coupling and prompt release of O D products observed as anisotropic velocity map images. This sensitive detection scheme will enable study of its unimolecular and bimolecular reactions under atmospheric conditions.
PMID: 31446755 [PubMed - as supplied by publisher]
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