Journal article

Authors list: Rummel, L; Hanke, K; Becker, J; Schreiner, PR

Publication year: 2023

Pages: 1129-1134

Journal: Accounts and Rapid Communications in Chemical Synthesis

Volume number: 34

Issue number: 10

ISSN: 0936-5214

eISSN: 1437-2096

DOI Link: https://doi.org/10.1055/a-1928-2473

Publisher: Thieme

Abstract: 
We 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.

Harvard Citation style: Rummel, L., Hanke, K., Becker, J. and Schreiner, P. (2023) London Dispersion Stabilizes Chloro-Substituted cis-Double Bonds, Accounts and Rapid Communications in Chemical Synthesis, 34(10), pp. 1129-1134. https://doi.org/10.1055/a-1928-2473

APA Citation style: Rummel, L., Hanke, K., Becker, J., & Schreiner, P. (2023). London Dispersion Stabilizes Chloro-Substituted cis-Double Bonds. Accounts and Rapid Communications in Chemical Synthesis. 34(10), 1129-1134. https://doi.org/10.1055/a-1928-2473