A series of imino- and amino-pyridine ligands based on dihydrobenzofurobenzofuran (BFBF) and methanodibenzodioxocine (DBDOC) backbones have been synthesized. These ligands form exclusively dinuclear complexes with metals such as iron(II) and copper(II). The structures for complexes 15, 16, 18, 19, 20, 21, 23, and 24 were determined by X-ray crystallography. The complexes show large distances for the metal nuclei and different geometries depending on the nature of the metal. An octahedral geometry was observed for the iron(II) complexes, while copper(II) complex 24 showed a distorted trigonal bipyramidal geometry. The iron(II) complexes showed activity as catalysts in the cycloaddition of CO2 to epoxides, obtaining moderate yields of cyclic carbonates.