Halide-Induced Supramolecular Ligand Rearrangement

A novel reaction involving the halide-induced rearrangement of ligands within supramolecular Rh(I) complexes containing hemilabile ligands is presented. Three analogous bis- and trishemilabile ligands have been synthesized to construct bi- and trimetallic Rh(I) macrocyclic complexes. An intentionally added halide source results in the formal rotation of only one hemilabile ligand along the axis that is perpendicular to the plane defined by the aryl backbone of the hemilabile ligands. X-ray structures, as determined by X-ray crystallography, of key intermediates and products are presented.