Density functional theory is used to explore the mechanisms of alkane hydroxylation for four synthetic non-heme iron(IV)-oxo complexes with three target substrates (Kaizer, J.; Klinker, E. J.; Oh, N. Y.; Rohde; J.-U.; Song, W. J.; Stubna, A.; Kim, J.; Münck, E.; Nam, W.; Que, L., Jr. J. Am. Chem. Soc. 2004, 126, 472-473; Rohde, J.-U.; Que, L., Jr. Angew. Chem. Int. Ed. 2005, 44, 2255-2258.). The iron-oxo reagents possess triplet ground states and low-lying quintet excited states. The set of experimental and theoretical reactivity trends can be understood if the reactions proceed on the two spin states, namely two-state reactivity (TSR); an appropriate new model is presented. The TSR model makes testable predictions: (a) If crossing to the quintet state occurs, the hydroxylation will be effectively concerted; however, if the process transpires only on the triplet surface, stepwise hydroxylation will occur, and side products derived from radical intermediates would be observed (e.g., loss of stereochemistry). (b) In cases of crossing en route to the quintet transition state, one expects kinetic isotope effects (KIEs) typical of tunneling. (c) In situations where the two surfaces contribute to the rate, one expects intermediate KIEs and radical scrambling patterns that reflect the two processes. (d) Solvent effects on these reactions are expected to be very large.