Iron(I) complexes of 2,9-bis(2-hydroxyphenyl)-1,10-phenanthroline (H₂dophen) as electrocatalysts for carbon dioxide reduction. X-ray crystal structures of [Fe(dophen)Cl]₂·2HCON(CH₃)₂ and [Fe(dophen)(N-MeIm)₂]ClO₄ (N-MeIm = 1-methylimidazole)

The crystal structure of two iron complexes of 2,9-bis(2-hydroxyphenyl)-1,10-phenanthroline (H2dophen) [Fe(dophen)Cl]2·2HCON(CH3)2 [1·2HCON(CH3)2] and [Fe(dophen)(N-MeIm)2]ClO4 [2] (N-MeIm = 1-methylimidazole) have been determined: 1·2HCON(CH3)2, monoclinic, space group P21/n, a = 11.141(4), b = 15.519(4), c = 13.387(3) Å, β = 93.76(2)°, Z = 4; 2, triclinic, space group P1̄, a = 10.293(1), b = 12.395(3), c = 12.400(6) Å, a = 105.04(4), β = 90.54(4), γ = 99.93(1)°, Z = 2. The cyclic voltammograms of 1 and 2 in dimethylformamide show that the iron complexes undergo three successive reversible reductions with E1/2 = -0.80 V, -2.02 V, -2.45 V for 1 and -0.75 V, -2.03 V and -2.45 V for 2 vs. the ferrocenium/ferrocene couple (Cp2Fe+/0) respectively. The first two couples are assigned as the Fe(III)/Fe(II) and Fe(II)/Fe(I) couples, whereas the couple at -2.45 V is assigned to the reduction of the dophen ligand. The Fe(I) species are active towards CO2 reduction. Electrolysis of CO2 in the presence of 1 or 2 at -2.0 V vs. Cp2Fe+/0 gave a mixture of carbon monoxide, formate and oxalate, with formate being the major product. The rate of CO2 reduction was enhanced by the addition of 1,1,1-trifluoroethanol or methanol as the proton source to the electrolyte. Iron carbonyl and iron formato species were detected as intermediates by in-situ FTIR spectroelectrochemistry.