2024/11/12 by Mark C. Elliott, Colan E. Hughes, Peter J. Knowles +1 · 3 voices
Chemistry · Engineering · #Electrochemical Analysis and Applications #Molecular Junctions and Nanostructures #Photochemistry and Electron Transfer Studies
paper · pdf · doi:10.1039/d4ob01572j
openalex publication_date 2024/11/12 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/02
It is commonly stated that alkyl groups exert an inductive electron-releasing effect when compared to hydrogen. This information has been given in numerous organic chemistry textbooks over the last 75 years. The evidence for this position is weak, and does not withstand scrutiny, and there is some evidence for the contrary position. We provide a significant body of computational data that clearly show that alkyl groups exert an inductive electron-withdrawing (-I) effect when compared to hydrogen. This revised position is not in conflict with experimental data, since alkyl group inductive effects are small and are likely to be masked by hyperconjugation/polarizability effects (particularly in charged species), and also by solvent effects.