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DOI: 10.1055/a-1928-2473
London Dispersion Stabilizes Chloro-Substituted cis-Double Bonds
This work was supported by the priority program ‘Control of London Dispersion in Molecular Chemistry’ (SPP1807) of the Deutsche Forschungsgemeinschaft.
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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.
Key words
double mutant cycle - equilibrium - hydrohalogenation - London dispersion - Pauli repulsionSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611940.
- Supporting Information
- CIF File
Publication History
Received: 07 July 2022
Accepted after revision: 19 August 2022
Accepted Manuscript online:
19 August 2022
Article published online:
30 September 2022
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