The Hydride‐Ion Affinity of Borenium Cations and Their Propensity to Activate H2 in Frustrated Lewis Pairs

Abstract

A range of frustrated Lewis pairs (FLPs) containing borenium cations have been synthesised. The catechol (Cat)-ligated borenium cation [CatB(PtBu(3))](+) has a lower hydride-ion affinity (HIA) than B(C(6)F(5))(3). This resulted in H(2) activation being energetically unfavourable in a FLP with the strong base PtBu(3). However, ligand disproportionation of CatBH(PtBu(3)) at 100 °C enabled trapping of H(2) activation products. DFT calculations at the M06-2X/6-311G(d,p)/PCM (CH(2)Cl(2)) level revealed that replacing catechol with chlorides significantly increases the chloride-ion affinity (CIA) and HIA. Dichloro-borenium cations, [Cl(2)B(amine)](+), were calculated to have considerably greater HIA than B(C(6)F(5))(3). Control reactions confirmed that the HIA calculations can be used to successfully predict hydride-transfer reactivity between borenium cations and neutral boranes. The borenium cations [Y(Cl)B(2,6-lutidine)](+) (Y = Cl or Ph) form FLPs with P(mesityl)(3) that undergo slow deprotonation of an ortho-methyl of lutidine at 20 °C to form the four-membered boracycles [(CH(2){NC(5)H(3)Me})B(Cl)Y] and [HPMes(3)](+). When equimolar [Y(Cl)B(2,6-lutidine)](+)/P(mesityl)(3) was heated under H(2) (4 atm), heterolytic cleavage of dihydrogen was competitive with boracycle formation.