| Abstrakt: |
Methods rooted in the density functional theory and in the coupled cluster ansatz were employed to investigate the cycloaddition reactions to ethylene and acetylene of 1,3‐dipolar species including ozone and the derivatives issued from replacement of the central oxygen atom by the valence‐isoelectronic sulfur atom, and/or of one or both terminal oxygen atoms by the isoelectronic CH2 group. This gives rise to five different 1,3‐dipolar compounds, namely ozone itself (O3), sulfur dioxide (SO2), the simplest Criegee intermediate (CH2OO), sulfine (CH2SO), and thioformaldehyde S‐methylide (CH2SCH2, TSM). The experimental and accurate theoretical data available for some of those molecules were employed to assess the accuracy of two last‐generation composite methods employing conventional or explicitly correlated post‐Hartree‐Fock contributions (jun‐Cheap and SVECV‐f12, respectively), which were then applied to investigate the reactivity of TSM. The energy barriers provided by both composite methods are very close (the average values for the two composite methods are 7.1 and 8.3 kcal mol−1 for the addition to ethylene and acetylene, respectively) and comparable to those ruling the corresponding additions of ozone (4.0 and 7.7 kcal mol−1, respectively). These and other evidences strongly suggest that, at least in the case of cycloadditions, the reactivity of TSM is similar to that of O3 and very different from that of SO2. [ABSTRACT FROM AUTHOR] |
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