Synthesis and Characterization of the First (1, 2‐Benzenedithiolato)iron(III) Complexes with Tripodal Ligands

Abstract

Abstract The reaction of iron(III) perchlorate nonahydrate with the tripodal tetradentate ligand tris[(2‐pyridyl)methyl]amine (tpa) or bis[(2‐pyridyl)methyl][(1‐methylimidazol‐2‐yl)methyl]amine (bpia) and 1, 2‐benzenedithiolate (dtc) yields the iron(III) coordination compounds [Fe(tpa)(dtc)]ClO 4 ·0.25 MeOH (1) and [Fe(bpia)(dtc)]ClO 4 (2) , respectively. These are the first iron(III) complexes with tripodal ligands and dtc, resulting in a N 4 S 2 coordination environment. The new compounds were isolated and characterized by single crystal X‐ray crystallography as well as spectroscopic methods. Compound 1 crystallizes in the monoclinic space group P2 1 /c (No. 14) with a = 29.636(6), b = 12.502(3), c = 14.390(3)Å, β = 102.19(3)°, V = 5211(2)Å 3 , Z = 8. Compound 2 crystallizes in the orthorhombic space group P2 1 2 1 2 1 (No. 19) with a = 8.881(2), b = 16.155(3), c = 17.895(4)Å, V = 2567.4(9)Å 3 , Z = 4. Furthermore the new compound [Fe(tpa)(tcc)](ClO 4 )·0.25 H 2 O ( 3 ) (where tcc = tetrachlorocatecholate dianion) is presented and compared to the dithiolato complexes. 3 crystallizes in the monoclinic space group P2 1 /c (No. 14) with a = 8.982(1)Å, b = 34.329(6)Å, c = 8.648(1)Å, β = 94.22(1)°, V = 2659.3(6)Å 3 , Z = 4.