Project Details
Projekt
London Dispersion in Brønsted Acid Catalysis
Applicant
Professorin Dr. Ruth M. Gschwind
Subject Area
Organic Molecular Chemistry - Synthesis and Characterisation
Term
from 2018 to 2023
Project identifier
Deutsche Forschungsgemeinschaft (DFG) - Project number 397981750
The assessment of dispersion interactions in the transition states of stereoselective catalysis is a very valuable but challenging task, which is so far mainly based on theoretical calculations. For the chiral BINOL-based phosphoric acids used in Brønsted acid catalysis strong contributions of dispersion interactions are expected in their stereodecisive transition states. However to our knowledge an experimental set-up to measure the role of these dispersion interactions is still missing. Recently, we got a detailed insight into the structures and hydrogen bond properties of the binary complexes of chiral phosphoric acids with imines. In addition, we developed the DTS-hn method (decrypting transition states with light) the first experimental access to active transition state combinations and applied it to the transferhydrogenation of imines using chiral phosphoric acids. In this project now the relative dispersion donor energies of various imine/chiral phosphoric catalyst pairs in their ground state structures shall be experimentally measured using dispersion energy balances. Three different experimental dispersion balances and accompanying theoretical calculations are planned to assess contributions from solvent effects, potential changes in the H-bonds or experimental error. The derived dispersion energy values will be compared to the synthetic results of the catalyses and interpreted with the help of the DTS-hn method and theoretical calculations. Overall this combined experimental and theoretical approach is expected to give an assessment of the importance of dispersion interactions in the transition states of Brønsted acid catalysis as well as of their potential changes between ground state and transition state structures.
DFG Programme
Priority Programmes
