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

ABSTRACT: Complexes of the Lewis base-free cations (^MeBDI)Mg⁺ and ( ^tBuBDI)Mg⁺ with Ph-X ligands (X = F, Cl, Br, I) have been studied (^MeBDI = HC[C(Me)N-DIPP]₂ and ^tBuBDI = HC[C(tBu)N-DIPP]₂; DIPP = 2,6-diisopropylphenyl). For the smaller β-diketiminate ligand (^MeBDI) only complexes with PhF could be isolated. Heavier Ph-X ligands could not compete with bonding of Mg to the weakly coordinating anion B(C₆F₅)₄ ^-. For the cations with the bulkier ^tBuBDI 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.

SUBMITTER: Friedrich A 

PROVIDER: S-EPMC8179342 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature