Femtosecond x-ray pump-x-ray probe experiments are currently possible at free electron lasers such as the linac coherent light source, which opens new opportunities for studying solvated transition metal complexes. In order to make the most effective use of these kinds of experiments, it is necessary to determine which chemical properties an x-ray probe pulse will measure. We have combined electron cascade calculations and excited-state time-dependent density functional theory calculations to predict the initial state prepared by an x-ray pump and the subsequent x-ray probe spectra at the Fe K-edge in the solvated model transition metal complex, K4FeII(CN)6. We find several key spectral features that report on the ligand-field splitting and the 3p and 3d electron interactions. We then show how these features could be measured in an experiment.