Analysis of Problematic Complexing Behavior of Ferric Chloride with N,N-Dimethylformamide Using Combined Techniques of FT-IR, XPS, and TGA/DTG

A problematic coordination behavior of highly hygroscopic FeCl(3) in DMF solution was studied. From the compositional and structural analyses for the adduct of FeCl(3)/DMF using various techniques such as FTIR, elemental analysis, UV/vis, XPS, and TGA/DTG, it was found that the iron cation exists in the form of an Fe(3+) cation and coordinates via the carbonyl oxygen atom of amide bond in DMF. The analyses of both FT-IR and XPS C 1s spectra for the adduct revealed that 2.1 molecules of DMF coordinate with a more electron-deficient Fe(3+); otherwise 1.2 molecules of DMF coordinated with a relatively electron-rich Fe(3+). The Cl 2p spectrum indicated that the electron-deficient Fe(3+) coordinated with two chlorine ions and the electron-rich Fe(3+) with four chlorines so that the chemical formula of the adduct is of FeCl(2)(DMF)(1.2)(H(2)O)(2.7)(+)FeCl(4)(DMF)(2.1)(-). The water molecules in the adduct were found chemisorbed rather than physisorbed, with a singular binding energy.