A coupled-cluster approach to the relative strains in [1.1.1]propellane,its derivatives and hetero[1.1.1]propellanes

The molecule 1.1.1]propellane and its neutral boron, nitrogen, oxygen, sulphur, S–O, and SO₂ analogs as well as the methyl, hexafluoro, and tri-carbonyl substituted derivatives have been investigated by theoretical calculations at the coupled-cluster singles and doubles level with an augmented polarized double zeta basis set. The geometries were optimized and vibrational analysis was carried out for each species. The main objective of this study was to determine the relative strain in these systems, which in turn is a predictor of stability and reactivity providing valuable information about potentially viable synthetic targets. The systems with the least strain are the nitrogen, boron and the S–O analogs, whereas the SO₂ substituted molecule and the hexafluoride and tricarbonyl substituted analogs exhibited the largest amount of strain. Geometrical features are also investigated and it is demonstrated that non-bonded repulsive interactions contribute significantly to the strain in some of the systems since cage-like structures force relatively short non-bonded distances.