Solution photochemistry of (mu-pdt)[Fe(CO)(3)](2) (pdt = mu(2)-S(CH2)(3)S), a precursor model of the 2-Fe subsite of the H-cluster of the hydrogenase enzyme, has been studied using time-resolved infrared spectroscopy. Following the loss of CO, solvation of the Fe center by the weakly binding ligands cyclohexene, 3-heicyne, THF, and 2,3-dihydrofuran (DHF) occurred. Subsequent ligand substitution of these weakly bound ligands by pyridine or cyclooctene to afford a more stable complex was found to take place via a dissociative mechanism on a seconds time scale with activation parameters consistent with such a pathway. That is, the Delta S double dagger values were positive and the Delta H double dagger parameters closely agreed with bond dissociation enthalpies (BDEs) obtained from DFT calculations. For example, for cyclohexene replacement by pyridine, experimental Delta H double dagger and Delta S double dagger values were determined to be 19.7 +/- 0.6 kcal/mol (versus a theoretical prediction of 19.8 kcal/mol) and 15 +/- 2 eu, respectively. The ambidentate ligand 2,3-DHF was shown to initially bind to the iron center via its oxygen atom followed by an intramolecular rearrangement to the more stable eta(2)-olefin bound species. DFT calculations revealed a transition state structure with the iron atom almost equidistant from the oxygen and one edge of the olefinic bond. The computed Delta H double dagger of 10.7 kcal/mol for this isomerization process was found to be in excellent agreement with the experimental value of 11.2 +/- 0.3 kcal/mol.