Dispersion Energy‐Stabilized Boron and Phosphorus Lewis Pairs

Abstract

An isostructural series of boron/phosphorus Lewis pairs was systematically investigated. The association constants of the Lewis pairs were determined at variable temperatures, enabling the extraction of thermodynamic parameters. The stabilization of the Lewis adduct increased with increasing size of the dispersion energy donor groups, although the donor and acceptor properties of the Lewis pairs remained largely unchanged. This data was utilized to challenge state‐of‐the‐art quantum chemical methods, which finally led to an enhanced workflow for the determination of thermochemical properties of weakly bound Lewis pairs within an accuracy of 0.6 to 1.0 kcal mol−1 for computed association free energies.

Ir(I)–Bi(III) Donor–Acceptor Adducts Stabilized by Dispersion Interactions between the Metal Pincer Ligands and Their Possible Self-Assembly Forming Molecular 1D Semiconductors

“…Thus, the binding energy of the 1A structure is roughly equal to Δ E disp and thus, 1A can be considered as a dispersion-stabilized adduct. Dispersion energy stabilized Lewis pairs were observed recently, e.g., for the binding of boron and phosphorus compounds …”

“…Dispersion energy stabilized Lewis pairs were observed recently, e.g., for the binding of boron and phosphorus compounds. 21 The decisive role of the ΔE disp stabilization can be also supported by the fact that the structure 1A is flexible with respect to the Bi−Ir bond elongation. The increase of the Bi−Ir distance by 0.317 Å up to 3.0 Å is connected with the energy penalty of 4.1 kcal/mol (Table S2), i.e., only ca.…”