Role of London Dispersion Interactions in Ga-Substituted Dipnictenes

We report the synthesis and structural characterization of Ga-substituted diarsene [L­(EtO)­GaAs]2, which is an exemplary case of a Ga-substituted dipnictene of the general type [L­(X)­Ga]2E2 (L = C­[C­(Me)­N­(2,6-i-Pr2-C6H3)]2, X = F, Cl, Br, I, NMe2, OEt; E = As, Sb, Bi). We examined this extended series of compounds computationally and found that attractive London dispersion interactions between the substituents on the N,N′-chelating β-diketiminate ligands as well as pnictogen−π interactions between the group 15 metal center and the ligand are key factors for the stability and the electronic structures of such types of complexes.