Dispersion Energy-Stabilized Boron and Phosphorus Lewis Pairs.

Area of Science:

• * Inorganic Chemistry
• * Computational Chemistry
• * Physical Chemistry

Background:

• * Lewis pairs are crucial in chemical bonding and catalysis.
• * Understanding their thermochemical properties is essential for predicting reactivity.
• * Existing computational methods require refinement for weakly interacting systems.

Purpose of the Study:

• * To systematically investigate an isostructural series of boron/phosphorus Lewis pairs.
• * To determine the thermodynamic parameters governing their association.
• * To enhance the accuracy of computational methods for thermochemical property determination.

Main Methods:

• * Synthesis and characterization of an isostructural series of Lewis pairs.
• * Measurement of association constants at variable temperatures.
• * Application and refinement of quantum chemical methods.

Main Results:

• * Lewis pair stabilization correlated with the size of dispersion energy donor groups.
• * Donor and acceptor properties of the Lewis pairs remained consistent.
• * Developed an enhanced workflow for computing thermochemical properties.

Conclusions:

• * Dispersion forces play a significant role in stabilizing Lewis adducts.
• * The refined computational workflow achieves high accuracy (0.6–1.0 kcal mol⁻¹) for association free energies.
• * This work provides a more reliable method for studying weakly bound Lewis pairs.