Understanding the Role of Dispersion in Frustrated Lewis Pairs and Classical Lewis Adducts: A Domain‐Based Local Pair Natural Orbital Coupled Cluster Study

• Published in: Chemistry : a European journal 2017-01, Vol.23 (4), p.865-873
• Main Authors: Bistoni, Giovanni, Auer, Alexander A., Neese, Frank
• Format: Article
• Language: English
• Subjects: Adducts; Chemistry; Decomposition; density functional calculations; Dispersion; Dissociation energy; Energy of dissociation; Lewis acid; Lewis acids; Lewis bases; Monomers; Phosphines; structure–activity relationships; substituent effects
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201604127

The interaction of Lewis acids and bases in both classical Lewis adducts and frustrated Lewis pairs (FLPs) is investigated to elucidate the role that London dispersion plays in different situations. The analysis comprises 14 different adducts between tris(pentafluorophenyl)borane and a series of phosphines, carbenes, and amines with various substituents, differing in both steric and electronic properties. The domain‐based local pair natural orbital coupled‐cluster (DLPNO‐CCSD(T)) method is used in conjunction with the recently introduced local energy decomposition (LED) analysis to obtain state‐of‐the‐art dissociation energies and, at the same time, a clear‐cut definition of the London dispersion component of the interaction, with the ultimate goal of aiding in the development of designing principles for acid/base pairs with well‐defined bonding features and reactivity. In agreement with previous DFT investigations, it is found that the London dispersion dominates the interaction energy in FLPs, and is also remarkably strong in Lewis adducts. In these latter systems, its magnitude can be easily modulated by modifying the polarizability of the substituents on the basic center, which is consistent with the recently introduced concept of dispersion energy donors. By counteracting the destabilizing energy contribution associated with the deformation of the monomers, the London dispersion drives the stability of many Lewis adducts. Interactions decomposed: The DLPNO‐CCSD(T) local energy decomposition analysis is used to elucidate the nature of the interaction in frustrated Lewis pairs and classical Lewis adducts. London dispersion is a fundamental component of structural stability in both cases (see figure). In acid–base adducts, its magnitude can be tuned by modifying substituents close to the basic center.