LAUSR

A theoretical study concerning key factors affecting activation energies for ring-opening reactions of tetrahydrofuran (THF) by G13/P-based (G13 = B, Al, Ga, In, and Tl) and Al/G15-based (G15 = N, P, As, Sb, and Bi) frustrated Lewis pairs (FLPs) featuring the dimethylxanthene scaffold was performed using density functional theory. Our theoretical findings indicate that only dimethylxanthene backbone Al/P-Rea (Rea = reactant) FLP-type molecules can be energetically favorable to undergo the ring-opening reaction with THF. Our theoretical evidence reveals that the shorter the separating distance between Lewis acidic (LA) and Lewis basic (LB) centers of the dimethylxanthene backbone FLP-type molecules, the greater the orbital overlaps between the FLP and THF and the lower the activation barrier for such a ring-opening reaction. Energy decomposition analysis (EDA) evidence suggests that the bonding interaction for such a ring-opening reaction is predominated by the donor–acceptor interaction (singlet–singlet interaction) compared to the electron-sharing interaction (triplet–triplet interaction). In addition, the natural orbitals for chemical valence (NOCV) evidence demonstrate that the bonding situations of such ring-opening reactions can be best described as FLP-to-THF forward bonding (the lone pair (G15) → the empty σ*(C–O)) and THF-to-FLP back bonding (the empty σ*(G13) ← filled p-π(O)). The EDA-NOCV observations show that the former plays a predominant role and the latter plays a minor role in such bonding conditions. The activation strain model reveals that the deformation energy of THF is the key factor in determining the activation energy of their ring-opening reactions. Comparing the geometrical structures of the transition states with their corresponding reactants, a linear relationship between them can be rationally explained by the Hammond postulate combined with the respective activation barriers calculated in this work.