Synthetic investigations of the diisocyanide‐bridged Cp*‐cobalt rectangles

Abstract

This study explores the utilization of 1,4‐diisocyanobenzene as a linear bridging ligand for the assembly of organometallic CpCo or Cp*Co complexes. Overcoming solubility challenges, the synthesis of organometallic Cp* cobalt complexes incorporating bridging 1,4‐diisocyanobenzene ligands was successfully achieved, while similar CpCo complexes were not attainable. The presented approach encompasses investigations into both stepwise and self‐assembly synthetic pathways, leading to the construction of a rectangular tetranuclear complex [(Cp*CoI)4(μ‐1,4‐CNC6H4NC)4](OTf)4 (3). Through single‐crystal x‐ray diffraction and spectroscopic techniques such as infrared, nuclear magnetic resonance, and electrospray ionization‐mass spectrometry, the cobalt‐isocyanides complexes were characterized.