Transition-Metal Complexes with Ferrocene-Bridged Bis(imidazolin-2-imine) and Bis(diaminocyclopropenimine) Ligands

Abstract

The reaction of the ferrocene-bridged bis(imidazolin-2-imine) ligand N,N′-bis(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)-1,1′-ferrocenediamine [fc(NIm)2] with MCl2salts furnished the complexes [{fc(NIm)2}MCl2] (M = Mn, Fe, Co, Ni, Cu, Zn), which were structurally and spectroscopically characterized. The iron complex was oxidized by reaction with ferrocenium hexafluoroantimonate, and both compounds, [{fc(NIm)2}FeCl2] and [{fc(NIm)2}FeCl2]SbF6, were further studied by means of Mössbauer spectroscopy, SQUID magnetometry, and single-crystal X-ray diffraction, revealing that oxidation occurred at the tetrahedral FeN2Cl2moiety. The CuX (X = Cl, Br, I) complexes of fc(NIm)2were synthesized, affording dimeric (X = Cl, Br) or polymeric (X = I) structures. In addition, the ligand bis(N,N,N′,N′-tetraisopropyl-2,3-diaminocyclopropen-1-ylidene)-1,1′-ferrocenediamine [fc(NCyp)2], was prepared and the trimetallic complex [{fc(NCyp)2}Pd2Cl4] was synthesized and structurally characterized. The attempted synthesis of the corresponding nickel complex furnished single crystals of the composition [{fc(NHCyp)2}Cl(NiCl3)]; X-ray diffraction analysis afforded the first crystal structure of the [Ni2Cl6]2–anion.