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

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 MCl 2 salts furnished the complexes [{fc(NIm) 2 }MCl 2 ] (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 }FeCl 2 ] and [{fc(NIm) 2 }FeCl 2 ]SbF 6 , were further studied by means of Mössbauer spectroscopy, SQUID magnetometry, and single‐crystal X‐ray diffraction, revealing that oxidation occurred at the tetrahedral FeN 2 Cl 2 moiety. The CuX (X = Cl, Br, I) complexes of fc(NIm) 2 were 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 }Pd 2 Cl 4 ] was synthesized and structurally characterized. The attempted synthesis of the corresponding nickel complex furnished single crystals of the composition [{fc(NHCyp) 2 }Cl(NiCl 3 )]; X‐ray diffraction analysis afforded the first crystal structure of the [Ni 2 Cl 6 ] 2– anion.