Use of 5,10‐Disubstituted Dibenzoazaborines and Dibenzophosphaborines as Cyclic Supports of Frustrated Lewis Pairs for the Capture of CO(2)

The reactivity of 5,10‐disubstituted dibenzoazaborines and dibenzophosphaborines towards carbon dioxide was studied at the DFT, M06‐2X/def2‐TZVP, computational level. The profile of this reaction comprises of three stationary points: the pre‐reactive complex and adduct minima and the transition state(TS) linking both minima. Initial results show that dibenzoazaborines derivatives are less suitable to form adducts with CO(2) than dibenzophosphaborine systems. The influence of the basicity on the P atom and the acidity on the B center of the dibenzophosphaborine in the reaction with CO(2) was also explored. Thus, an equation was developed relating the properties (acidity, basicity and boron hybridization) of the isolated dibenzophosphaborine derivatives with the adduct energy. We found that modulation of the boron acidity allows to obtain more stable adducts than the pre‐reactive complexes and isolated monomers.