London Dispersion Stabilizes Chloro-Substituted cis-Double Bonds

Abstract

AbstractWe present a combined experimental and computational study on the thermodynamic stability of cis- and trans-alkenes substituted with dispersion energy donor (DED) groups. To investigate the role of noncovalent interactions on equilibrium of cis- and trans-alkenes we utilized hydrochlorination reactions. While the general assumption is that increasing steric bulk favors the trans-alkene, we observe an equilibrium shift towards the more crowded cis-alkene with increasing substituent size. With the aim to quantify noncovalent interactions, we performed a double mutant cycle to experimentally gauge the attractive potential of bulky substituents. Additionally, we utilized local energy decomposition analysis at the DLPNO-CCSD(T)/def2-TZVP level of theory. We found LD interactions and Pauli exchange repulsion to be the most dominant components to influence cis- and trans-alkene equilibria.