Infrared Spectra of (Z)- and (E)-•CH2C(CH3)CHI Radicals Produced upon Photodissociation of (Z)- and (E)-(CH2I)(CH3)C═CHI in Solid para-Hydrogen.

Ozonolysis of isoprene is important in atmospheric chemistry because of the abundant emission of isoprene. This process produces the Criegee intermediates CH2OO, methyl vinyl ketone oxide (MVKO, C2H3C(CH3)OO), and methacrolein oxide (MACRO, CH2C(CH3)CHOO). Gaseous MACRO was recently produced and identified in laboratories after photolysis of a mixture of 1,3-diiodo-2-methyl-prop-1-ene [(CH2I)(CH3)C═CHI] and O2, but the conformation-dependent formation mechanism remains unexplored. We report conformation-distinct IR spectra of (E)- and (Z)-(CH2I)(CH3)C═CHI isolated in solid p-H2. Upon irradiation near 300 nm of (E)- and (Z)-(CH2I)(CH3)C═CHI in solid p-H2 at 3.3 K, 3-iodo-2-methyl-prop-1-en-3-yl [•CH2C(CH3)CHI] radicals were characterized, with intense infrared absorption lines at 2991.3, 1458.7, 1434.7, 1317.4, 1190.4, 786.3, 677.9, and 467.2 cm-1 and additional 11 weaker ones assigned to (E)-•CH2C(CH3)CHI and intense lines at 3108.5, 3076.2, 3028.5, 2970.0, 1174.2, 796.0, 683.6, and 609.5 cm-1 and additional 7 weaker ones to (Z)-•CH2C(CH3)CHI. The assignments were derived according to the behaviors of secondary photolysis at 495 and 460 nm and a comparison of the vibrational wavenumbers and IR intensities of the observed lines with those calculated with the B2PLYP-D3/aug-cc-pVTZ-pp method. These observations confirm that only the allylic C-I bond, not the vinylic one, was photodissociated at 290 nm, and in solid p-H2, the excess energy upon photolysis induced no conformational change. When O2 was present in the matrix, several intense lines at 1147.5, 1025.7, 914.4, and 728.7 cm-1, and 4 weaker ones were tentatively assigned to the adduct CH2C(CH3)CHIOO; the assignments were supported by 18O2 isotopic experiments. Unlike in the gaseous phase, the remaining C-I bond of this adduct could not break to form MACRO because of the efficient quenching in a low-temperature matrix.

Formation reaction mechanism and infrared spectra of anti-trans-methacrolein oxide and its associated precursor and adduct radicals.

Methacrolein oxide (MACRO) is an important carbonyl oxide produced in ozonolysis of isoprene, the most abundantly-emitted non-methane hydrocarbon in the atmosphere. We employed a step-scan Fourier-transform infrared spectrometer to investigate the source reaction of MACRO in laboratories. Upon UV irradiation of precursor CH2IC(CH3)CHI (1), the CH2C(CH3)CHI radical (2) was detected, confirming the fission of the allylic C‒I bond rather than the vinylic C‒I bond. Upon UV irradiation of (1) and O2 near 21 Torr, anti-trans-MACRO (3a) was observed to have an intense OO-stretching band near 917 cm-1, much greater than those of syn-CH3CHOO and (CH3)2COO, supporting a stronger O‒O bond in MACRO because of resonance stabilization. At increased pressure (86‒346 Torr), both reaction adducts CH2C(CH3)CHIOO (4) and (CHI)C(CH3)CH2OO (5) radicals were observed, indicating that O2 can add to either carbon of the delocalized propenyl radical moiety of (2). The yield of MACRO is significantly smaller than other carbonyl oxides.