The Spectrum from van der Waals to Donor–Acceptor Bonding

Abstract

The chemical bond between halogenated borane Lewis acids and a variety of Lewis bases of varying strength (from strong to weak: NH₃, MeCN, N₂) has been quantum chemically explored using dispersion-corrected relativistic density functional theory (DFT) at ZORA-BLYP-D3(BJ)/TZ2P. We propose a unified picture of chemical bonding that exists on a continuum where weaker van der Waals (commonly referred to as “noncovalent”) interactions at longer distances transition into stronger donor–acceptor (commonly referred to as covalent) complexes at shorter distances. Remarkably, depending on the strength of the Lewis base, an intermediate regime is observed where both van der Waals and donor–acceptor complexes are observed. This study demonstrates that a covalent component is ubiquitous across the bonding spectrum, with the stability of the minima on potential energy surfaces determined by the strength of the Lewis acid-base interaction. We advocate for classifying Lewis pairs as strongly or weakly bonded based on whether their covalent interaction is strong enough to overcome the geometric penalty of bond formation. This work elucidates the fuzzy boundaries within chemical bonding.