Terpene dispersion energy donor ligands in borane complexes

Abstract

Structural characterization of the complex [B(β-pinane)₃] (1) reveals non-covalent H⋯H contacts that are consistent with the generation of London dispersion energies involving the β-pinane ligand frameworks. The homolytic fragmentations of 1, and camphane and sabinane analogues ([B(camphane)₃] (2) and [B(sabinane)₃] (3)) were studied computationally. Isodesmic exchange results showed that London dispersion interactions are highly dependent on the terpene's stereochemistry, with the β-pinane framework providing the greatest dispersion free energy (ΔG = −7.9 kcal mol⁻¹) with Grimme's dispersion correction (D3BJ) employed. PMe₃ was used to coordinate to [B(β-pinane)₃], giving the complex [Me₃P–B(β-pinane)₃] (4), which displayed a dynamic coordination equilibrium in solution. The association process was found to be slightly endergonic at 302 K (ΔG = +0.29 kcal mol⁻¹).