Classical conformational analysis of strained organic molecules. I. [l,m,n]Propellanes with l,m,n equal to 2, 3, and 4

Classical conformational analysis was applied to the study of the variation of heats of formation (HOF ) and geometrical parameters of small-ring propellanes. As expected, the calculated HOF is the smallest for [4,4,4] propellane I and the largest for [2,2,2]propellane X. In spite of the different trends exhibited by the strain energy components, the calculated HOF values may be reproduced within a simple additivity scheme. The calculated bridgehead–bridgehead bond length is the longest for [2,2,2]propellane (1.655 Å), lowers with increasing molecular size, and is equal to 1.558 Å for [4,4,4]propellane. In agreement with experimental findings the latter value is significantly larger than the standard value of 1.54 Å typical for unstrained hydrocarbons. Other calculated geometrical parameters as well as HOF values cannot be compared with experimental and/or theoretical results since there is a lack of reliable experimental data. Surprisingly, [2,2,2]propellane was found to be more flexible than the less strained bicyclo[2,2,2]octane.