Long but Strong C-C Single Bonds: Challenges for Theory

Theoretical challenges in describing molecules with anomalously long single C-C bonds are analyzed in terms of the relative contributions of stabilizing and destabilizing intramolecular interactions. Diamondoid dimers that are stable despite the presence of C-C bonds up to 1.7 Å long, as well as other bulky molecules stabilized due to intramolecular noncovalent interactions (London dispersions) are discussed. The unexpected stability of highly crowded molecules, such as diamondoid dimers and tert-butyl-substituted hexaphenylethanes, calls for reconsideration of the "steric effect" traditionally thought to destabilize the molecule. Alternatively, "steric attraction" helps to understand bonding in sterically overloaded molecules, whose structural and energetic analysis requires a proper theoretical description of noncovalent interactions.