F. Matthias Bickelhaupt

Feb 6, 2024 | pubs.rsc.org | F. Matthias Bickelhaupt

What defines electrophilicity in carbonyl compounds The origin of the electrophilicity of a series of cyclohexanones and benzaldehydes is investigated using the activation strain model and quantitative Kohn-Sham molecular orbital (MO) theory. We find that this electrophilicity is mainly determined by the electrostatic attractions between the carbonyl compound and the nucleophile (cyanide) along the entire reaction coordinate.

Jul 3, 2023 | nature.com | Jordi Poater |Pascal Vermeeren |Trevor A. Hamlin |F. Matthias Bickelhaupt

arising from S. Sowlati-Hashjin et al. Nature Communications https://doi.org/10.1038/s41467-022-29504-0 (2022)Recently, Sowlati-Hashjin et al.1 concluded that the nature of the Li–C chemical bond in LiCF3 differs significantly from that in LiCPh3 (Ph = phenyl).

Jun 20, 2023 | chemistry-europe.onlinelibrary.wiley.com | Thomas Hansen |Pascal Vermeeren |F. Matthias Bickelhaupt |Trevor A. Hamlin

Abstract We have quantum chemically studied the influence of ring strain on the competition between the two mechanistically different SN2 and E2 pathways using a series of archetypal ethers as substrate in combination with a diverse set of Lewis bases (F–, Cl–, Br–, HO–, H3CO–, HS–, H3CS–), using relativistic density functional theory at ZORA-OLYP/QZ4P. The ring strain in the substrate is systematically increased on going from a model acyclic ether to a 6- to 5- to 4- to 3-membered ether ring.