How Strained are Carbomeric-Cycloalkanes?

The ring strain energies of carbomeric-cycloalkanes (molecules with one or more acetylene spacer units placed into carbon single bonds) are assessed using a series of isodesmic, homodesmotic, and hyperhomodesmotic chemical equations. Isodesmic bond separation reactions and other equations derived from the explicitly defined hierarchy of homodesmotic equations are insufficient for accurately determining these values, since not all perturbing effects (i.e., conjugation and hyperconjugation) are fully balanced. A set of homodesmotic reactions is proposed, which succeeds in balancing all stereoelectronic effects present within the carbomeric rings, allowing for a direct assessment of the strain energies. Values calculated from chemical equations are validated using an increment/additivity approach. The ring strain energy decreases as acetylene units are added, manifesting from the net stabilization gained by opening the C−CH2−C angle around the methylene groups and the destabilization arising from bending the C−C≡C angles of the spacer groups. This destabilization vanishes with increasing parent ring size (i.e., the angle distortion is less in the carbomeric-cyclobutanes than in the carbomeric-cyclopropanes), leading to strain energies near zero for carbon-cyclopentanes and carbon-cyclohexanes.