The behavior of bisumanenyl is dynamic as a result of inversion of each of its sumanene bowls and rotation between the two bowls. This behavior was fully elucidated by a combination of NMR experiments and density functional theory calculations. The MM (or PP) and MP diastereomers are in thermodynamic equilibrium at room temperature and the MM (PP) diastereomer is 1.4-1.9kcalmol-1 more stable than MP diastereomer. The calculated energy for inversion between the two forms of the bowl is 19.2kcalmol-1. The MM (PP) and MP diastereomers have two rotational stable conformers that rapidly interconvert as a result of the low rotational energy barriers, which were calculated to be 3.9 and 8.9kcalmol-1, respectively.
ASJC Scopus subject areas
- Organic Chemistry