Abstract
Boron compounds usually exhibit Lewis acidity at the boron center due to the presence of vacant p-orbitals. We show that this chemistry can be altered by an appropriate choice of ligands to decorate the boron center. To elucidate this effect, we studied the interactions of boron with two classes of ligands, one based on penta-substituted phenyl species (C6X5, X = F, BO, CN) and the other based on Zintl-ion-based groups (Ge9Y3, Y = H, CH3, BO, CN). An in-depth analysis of the charges and Fukui function values at the local atomic sites of the substituted boron derivatives B(C6X5)3 and B[Ge9Y3]3 shows that the B-center in the former is electrophilic, while it is nucleophilic in the latter. The chemical stability of the B[Ge9Y3]3 species is shown to be due to the presence of strong 2c-2e bonds between the B and Ge centers. Thus, the general notion of the Lewis acid nature of a boron center depends upon the choice of the ligand.
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