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.