London Dispersion in Molecular Chemistry-Reconsidering Steric Effects

• Published in: Angewandte Chemie International Edition 2015-10, Vol.54 (42), p.12274-12296
• Main Authors: Wagner, J. Philipp, Schreiner, Peter R.
• Format: Article
• Language: English
• Subjects: Attraction; Catalysis; Catalysts; density functional theory; Dispersions; Molecular chemistry; Molecular structure; noncovalent interactions; Perception; Stability; Steric effects; Structural stability; van der Waals forces; weak interactions
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201503476

London dispersion, which constitutes the attractive part of the famous van der Waals potential, has long been underappreciated in molecular chemistry as an important element of structural stability, and thus affects chemical reactivity and catalysis. This negligence is due to the common notion that dispersion is weak, which is only true for one pair of interacting atoms. For increasingly larger structures, the overall dispersion contribution grows rapidly and can amount to tens of kcal mol−1. This Review collects and emphasizes the importance of inter‐ and intramolecular dispersion for molecules consisting mostly of first row atoms. The synergy of experiment and theory has now reached a stage where dispersion effects can be examined in fine detail. This forces us to reconsider our perception of steric hindrance and stereoelectronic effects. The quantitation of dispersion energy donors will improve our ability to design sophisticated molecular structures and much better catalysts. Center of attraction: Dispersion attraction makes all the difference in the stability of molecular structures, reactivity, and the design of catalysts. Although small for one pair of interactions, dispersion grows rapidly as the molecular size increases.