Cyanoferrocenes as redox-active metalloligands for coordination-driven self-assembly

Abstract

Ferrocene-based Lewis bases have found utility as metalloligands in a wide variety of applications. The coordination chemistry of cyanoferrocenes however, is underexplored. Herein, we describe a new synthetic protocol for the generation of cyanoferrocenes. The coordination chemistry of these metalloligands to [Cu(NCMe)₄][PF₆], [(PPh₃)₂Cu(NCMe)₂][PF₆] and [(dppf)Cu(NCMe)₂][PF₆] salts has been explored, providing crystallographic evidence of cluster and polymeric forms of 1,1′- and 1,2-dicyanoferrocene complexes. The stability of the complexes and ligand dissociation were found to be strongly solvent-dependent.