Magnesium–halobenzene bonding: mapping the halogen sigma-hole with a Lewis-acidic complex

Complexes of the Lewis base-free cations ((Me)BDI)Mg(+) and ((tBu)BDI)Mg(+) with Ph–X ligands (X = F, Cl, Br, I) have been studied ((Me)BDI = HC[C(Me)N-DIPP](2) and (tBu)BDI = HC[C(tBu)N-DIPP](2); DIPP = 2,6-diisopropylphenyl). For the smaller β-diketiminate ligand ((Me)BDI) only complexes with PhF could be isolated. Heavier Ph–X ligands could not compete with bonding of Mg to the weakly coordinating anion B(C(6)F(5))(4)(−). For the cations with the bulkier (tBu)BDI ligand, the full series of halobenzene complexes was structurally characterized. Crystal structures show that the Mg⋯X–Ph angle strongly decreases with the size of X: F 139.1°, Cl 101.4°, Br 97.7°, I 95.1°. This trend, which is supported by DFT calculations, can be explained with the σ-hole which increases from F to I. Charge calculation and Atoms-In-Molecules analyses show that Mg⋯F–Ph bonding originates from electrostatic attraction between Mg(2+) and the very polar C(δ+)–F(δ−) bond. For the heavier halobenzenes, polarization of the halogen atom becomes increasingly important (Cl < Br < I). Complexation with Mg leads in all cases to significant Ph–X bond activation and elongation. This unusual coordination of halogenated species to early main group metals is therefore relevant to C–X bond breaking.