Stereogenic-at-Metal Ir(III) Complexes as Platforms for the Construction of Asymmetric Bimetallic Complexes

The stereochemical-at-metal complexes Δ- and Λ-[Ir(ppy)₂(^S,RL)]BF₄, where ^S,RL is a bpy ligand substituted at the 6-position with a chiral diamine or derivative thereof, have been prepared and fully characterized by a combination of empirical and theoretical methods. The differing solubility of the Δ and Λ parent diastereomers in acetone allowed their ready separation. Further functionalization of an external amino group occurred with complete retention of absolute configuration and gave systems capable of binding to a second metal. The facility to coordinate other metals was explored by using in situ ¹H NMR experiments with ZnI₂. Coordination shifts were seen in the ¹H NMR spectra, confirming the coordination of Zn(II) and showcasing the potential of the complexes as flexible platforms for the construction of asymmetric bimetallics.