Complex consequences: Substituent effects on metal⋯arylmethylium interactions

Metal complexation to aryl (Ph, Cp, cyclobutadienyl) methylium cations, radicals, and anions was investigated using hybrid density functional theory methods (B3LYP/LANL2DZ), with a focus on the effects of substituents. The results of these calculations, in which both geometric and energetic consequences of adding substituents were examined, indicate that metal–methylium interactions are most sensitive to substituent effects for complexed cations.

Metal complexation to aryl methylium cations, radicals, and anions was investigated using density functional theory methods, with a focus on the effects of substituents. Metal–methylium interactions are predicted to be most sensitive to substituent effects for complexed cations.Figure optionsDownload as PowerPoint slideHighlights
► Substituents modulate geometries of metal–methylium species.
► Substituents modulate barriers for rotation of methylium groups of metalmethylium species.
► Metal–methylium interactions are most sensitive to substituent effects for complexed cations.