Unraveling Lewis base substitution in <i>ansa</i>-type frustrated Lewis pairs: how N → P replacement redefines adduct stability and H₂ activation.

ABSTRACT: This study investigates, through quantum-chemical calculations, how replacing nitrogen with phosphorus in ansa-type frustrated Lewis pairs reshapes both the FLP-CLA equilibrium and H₂ activation thermodynamics. Energy decomposition analysis shows that the stabilization of ansa-phosphinoborane adducts arises mainly from steric relief, which compensates for weaker donor-acceptor interactions. For H₂ activation, the energetic effect of Lewis base substitution reaches up to 35.9 kcal mol^-1 and correlates directly with the proton affinity differences between the corresponding amines and phosphines. This correlation identifies proton affinity as a predictive descriptor of reactivity. By establishing how N → P substitution redefines the steric-electr

SUBMITTER: Barrales-Martinez C 

PROVIDER: S-EPMC12538387 | biostudies-literature | 2025 Oct

REPOSITORIES: biostudies-literature