Electronic Interactions in Ferrocene‐ and Ruthenocene‐Functionalized Tetraazamacrcocyclic Ligand Complexes of Fe II/III , Co II , Ni II , Cu II and Zn II

The syntheses of ferrocene- and ruthenocene-functionalized tetraazamacrocyclic ligands and their corresponding transition metal complexes are described. Reaction of N,N′-bis(2-aminoethyl)-1,3-propanediamine (2,3,2-tet) with 1,1′-diformylferrocene and 1,1′-diformylruthenocene produces the ligands fcmac and rcmac in 81−85% yield. Examination of their CuII, NiII, CoII, ZnII and FeII/III complexes by IR, UV/Vis, EPR and Mossbauer spectroscopy as well as by electrochemical studies suggests electronic communication between the two metal centers of each complex. The molecular structure of [CuII(fcmac)(FBF3)]BF4, determined by X-ray structure analysis, is reported and shows that the distance betwee…