Theoretical analysis of cooperative effects of small molecule activation by frustrated Lewis pairs

Abstract

The energy profiles of the activation reaction of small molecules (H₂, Br₂ and CO₂) with boron/phosphorus frustrated Lewis pairs (FLPs) have been calculated with dispersion corrected DFT (TPSS-D3). We have investigated the cooperative nature of the reactions by analyzing interaction energies in the ternary system and for reactant pairs. The non-additive contributions to the total interaction energy add to the driving force of the activation reaction, even at early stages of the process. We propose the isosurface representation of the many-body deformation density Δρ_mb as a qualitative tool to visualize cooperative, non-additive effects in complex chemical systems.