Turn: Weak Interactions and Rotational Barriers in Molecules—Insights from Substituted Butynes

Abstract

The nature of the bonding and a definite preference for an eclipsed geometry in several substituted but-2-ynes, including certain novel derivatives are uncovered and examined. In particular, we consider the molecular species R3C-C≡C-CR3 (where R= H, F, Cl, Br, I, and CN), their R3C-B≡N-CR3 analogues, and a few novel exo-bridge systems with intramolecular hydrogen bonds running parallel to the C-C≡C-C chain. In some cases, the potential energy surfaces are remarkably flat-so flat, in fact, that free rotation is predicted for those molecules at very low temperatures. A systematic investigation of the bonding in the halogenated butynes demonstrates that the eclipsed conformation actually becomes more stable relative to the staggered form as R becomes larger and less electron-withdrawing. The rotational barriers (the differences in energy between the eclipsed and staggered geometries) are magnified significantly, however, in a special case where selected R groups at the ends of the R3C-C≡C-CR'3 molecule form hydrogen bonds parallel to the C-C≡C-C core. In those systems, the hydrogen bonds serve as a weak locking mechanism that favors the eclipsed conformation. A comparison of HF and uncorrected DFT methods versus the MP2(full), CCSD(T), and other dispersion-corrected methods confirms that correlation accounts to a significant extent for barriers in substituted butyne compounds. In the hydrogen-bonded systems, the barriers are comparable to and larger in some cases than the barriers observed for the more extensively studied ethane molecule.