Versatile Reactivity of a Solvent-Coordinated Diiron(II) Compound: Synthesis and Dioxygen Reactivity of a Mixed-Valent FeIIFeIII Species

A new, DMF-coordinated, preorganized diiron compound [Fe2(N-Et-HPTB)­(DMF)4]­(BF4)3 (1) was synthesized, avoiding the formation of [Fe­(N-Et-HPTB)]­(BF4)2 (10) and [Fe2(N-Et-HPTB)­(μ-MeCONH)]­(BF4)2 (11), where N-Et-HPTB is the anion of N,N,N′,N′-tetrakis­[2-(1-ethylbenzimidazolyl)]-2-hydroxy-1,3-diaminopropane. Compound 1 is a versatile reactant from which nine new compounds have been generated. Transformations include solvent exchange to yield [Fe2(N-Et-HPTB)­(MeCN)4]­(BF4)3 (2), substitution to afford [Fe2(N-Et-HPTB)­(μ-RCOO)]­(BF4)2 (3, R = Ph; 4, RCOO = 4-methyl-2,6-diphenyl benzoate]), one-electron oxidation by (Cp2Fe)­(BF4) to yield a Robin–Day class II mixed-valent diiron­(II,III) compound, [Fe2(N-Et-HPTB)­(μ-PhCOO)­(DMF)2]­(BF4)3 (5), two-electron oxidation with tris­(4-bromophenyl)­aminium hexachloroantimonate to generate [Fe2(N-Et-HPTB)­Cl3(DMF)]­(BF4)2 (6), reaction with (2,2,6,6-tetramethylpiperidin-1-yl)­oxyl to form [Fe5(N-Et-HPTB)2(μ-OH)4(μ-O)­(DMF)2]­(BF4)4 (7), and reaction with dioxygen to yield an unstable peroxo compound that decomposes at room temperature to generate [Fe4(N-Et-HPTB)2(μ-O)3(H2O)2]­(BF4)·8DMF (8) and [Fe4(N-Et-HPTB)2(μ-O)4]­(BF4)2 (9). Compound 5 loses its bridging benzoate ligand upon further oxidation to form [Fe2(N-Et-HPTB)­(OH)2(DMF)2]­(BF4)3 (12). Reaction of the diiron­(II,III) compound 5 with dioxygen was studied in detail by spectroscopic methods. All compounds (1–12) were characterized by single-crystal X-ray structure determinations. Selected compounds and reaction intermediates were further examined by a combination of elemental analysis, electronic absorption spectroscopy, Mössbauer spectroscopy, EPR spectroscopy, resonance Raman spectroscopy, and cyclic voltammetry.