The syntheses and characterization of a series of iron(III) complexes of the ligand N, N′-bis(2-pyridylmethyl)ethane- 1,2-diamine (bispicen), C 14H 18N 4 are described. The monomeric complexes [(bispicen)FeCl 2]ClO 4 ( 1) and the corresponding chloride salt [(bispicen)FeCl 2]Cl ( 1a) have been isolated and the structure of the perchiorate salt ( 1) has been determined from three-dimensional crystallographic data. The complex crystallizes in space group P2 1/ c of the monoclinic system with four mononuclear species in a cell of dimensions a=7.323(2), b=14.370(3), c=18.103(4) Å, β=90.71(2)°. The structure has been refined to a final R factor of 0.0496 based on 2948 observed independent reflections. The central iron(III) atom is pseudo-octahedrally bonded to the four nitrogen atoms of the ligand and to two cis chloride ligands. The μ-oxodiiron(III) complex {[(bispicen)(Cl)Fe] 2(μ-O)}(I 3) 2 ( 2), C 28H 36Cl 2Fe 2I 6N 8O, crystallizes in space group P2 1/ n of the monoclinic system with two binuclear species in a cell of dimensions a = 8.570(2), b = 14.756(3), c = 17.083(3) Å, β = 99.68(2)°. The structure has been refined to a final R factor of 0.0417 based on 2272 observed independent reflections. The complex contains a linear FeOFe unit with FeO and Fe···Fe separations of 1.798(1) and 3.596(2) Å, respectively. The μ-oxo, μ-acetatodiiron(III) complex {[(bispicen)Fe] 2(μ-O)μ-OAc)}I 3·2H 2O (3), C 30H 43Fe 2I 3N 8O 5, crystallizes in space group P 1 of the triclinic system with two binuclear species in a cell of dimensions a = 10.785(2), b = 12.378(2), c = 15.834(2) Å, α = 87.060(10), β = 87.180(10), γ = 70.630(10)°. The structure has been refined to a final R factor of 0.0386 based on 4739 observed independent reflections. The complex contains a bent FeOFe unit with a bridging FeOFe angle of 129.8(2)° and associated average FeO and Fe···Fe separations of 1.794(1) and 3.248(2) Å, respectively. The FeO (acetato) distances are 2.009(3) and 2.040(4) Å. The μ-oxo, μ-carbonatodiiron(III) complex {[(bispicen)Fe] 2(μ- O)(μ-CO 3)}I 2·6H 2O ( 4), C 29H 48Fe 2I 2N 8O 10, also crystallizes in space group P 1 of the triclinic system with two binuclear species in a cell of dimensions a = 10.158(2), b = 13.459(2), c = 15.712(3) Å, α = 73.020(10), β = 85.290(10), γ = 79.230(10)°. The structure has been refined to a final R factor of 0.0348 based on 4294 observed independent reflections. The structure of the complex cation is very similar to that in 3, and contains a bent FeOFe unit with a bridging Fe OFe angle of 129.0(2)° and associated average FeO and Fe···Fe separations of 1.796(11) and 3.241(2) Å, respectively. The FeO (carbonato) distances are 1.962(4) and 1.963(4) Å. The binuclear complexes exhibit antiferromagnetic interactions with J values of −102.1, −118.2, and −113.6 cm −1 for 2, 3 and 4, respectively. The electronic spectra are similar to those observed in related species.