The addition reactions of chlorine atom with isobutene (i-CH) in solid para-hydrogen (p-H) were investigated with infrared (IR) absorption spectra. When a p-H matrix containing Cl and isobutene was irradiated with ultraviolet light at 365 nm, intense lines in a set at 534.5, 1001.0, 1212.9, 1366.0, 2961.6, and 2934.7 cm, and several weaker others due to the 1-chloro-2-methyl-2-propyl radical, C(CH)CHCl, and those in a second set including intense ones at 642.7, 799.2, 1098.2, 1371.8, and 3027.3 cm due to the 2-chloro-2-methylpropyl radical, CHC(CH)Cl, appeared; the ratio of C(CH)CHCl to CHC(CH)Cl was approximately (3 ± 1):1. The observed wavenumbers and relative intensities agree with the vibrational wavenumbers and IR intensities predicted with the B3PW91/aug-cc-pVTZ method. That the Cl atom adds to both carbons of the C=C bond of isobutene with the terminal site slightly favored is consistent with the energies of products predicted theoretically, but is in contrast to the reaction of Cl + propene in solid p-H in which the addition of Cl to mainly the central C atom was previously reported. The role of the p-H matrix in affecting the reaction paths is discussed. Absorption lines of the complex i-CH⋅Cl and the dichloro-product anti-1,2-dichloro-2-methylpropane, a-CHClCCl(CH), are also characterized.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.