Substituent Dependence on the Reactions of Criegee Intermediates with Carbon Dioxide and Carbon Monoxide

Abstract

AbstractCriegee intermediates (CIs), R1R2COO, are active molecules produced in the atmosphere from the ozonolysis of alkenes. Here, we systematically evaluated the reactivity of ten CIs with carbon monoxide and carbon dioxide using CCSD(T)‐F12/cc‐pVTZ‐F12//B3LYP/6‐311+G(2d,2p) energies and transition state theory. Many previous studies focused on alkyl substitution, but here we evaluated both alkyl and vinyl substitution toward the reactivity by studying five anti‐type CIs: CH2OO, anti‐CH3CHOO, anti‐cis‐C2H5CHOO, anti‐trans‐MACRO, anti‐cis‐MACRO; and five syn‐type CIs: syn‐CH3CHOO, (CH3)2COO, syn‐trans‐C2H5CHOO, syn‐trans‐MVKO, and syn‐cis‐MVKO. Our study showed that reactions involving CO2 have a large substituent dependence varying nearly five orders of magnitude, while those involving CO have a much smaller two orders of magnitude difference. Analysis based on the strain interaction model showed that deformation of the CI is an important feature in determining the reactivity with CO2. On the other hand, we used the OO and CO bond ratios to analyze the zwitterionic character of the CIs. We found that vinyl substitution with π‐conjugation results in smaller zwitterionic character and lower reactivity with CO. Lastly, the reactivity of CIs with CO as well as CO2 were found to be not fast enough to be important in an atmospheric context.