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X-ray absorption Fe-K edge data on ferrous and ferric model complexes have been studied to establish a detailed understanding of the 1s f 3d pre-edge feature and its sensitivity to the electronic structure of the iron site. The energy position and splitting, and intensity distribution, of the pre-edge feature were found to vary systematically with spin state, oxidation state, geometry, and bridging ligation (for binuclear complexes). A methodology for interpreting the energy splitting and intensity distribution of the 1s f 3d pre-edge features was developed for highspin ferrous and ferric complexes in octahedral, tetrahedral, and square pyramidal environments and low-spin ferrous and ferric complexes in octahedral environments. In each case, the allowable many-electron excited states were determined using ligand field theory. The energies of the excited states were calculated and compared to the energy splitting in the 1s f 3d pre-edge features. The relative intensities of electric quadrupole transitions into the manyelectron excited states were obtained and compared to the intensity pattern of the pre-edge feature. The effects of distorting the octahedral iron site to tetrahedral and square pyramidal geometries were analyzed. The contributions to the pre-edge intensity from both electric quadrupole and electric dipole (from 3d-4p mixing) intensity mechanisms were established for these distorted cases; the amount of 4p character and its distribution over the many-electron final states were experimentally estimated and compared to theoretical predictions from density functional calculations. The methodology was also applied to binuclear complexes, and a clear marker for the presence of a µ-oxo Fe-O-Fe bridge was established. General trends in 3d-4p mixing are developed and discussed for a series of geometries and oxidation states of Fe complexes. The results presented should further aid in the interpretation of the 1s f 3d pre-edge region of iron complexes and non-heme iron enzymes.