Iron(II) complexes of a series of N-acylated dipyridin-2-ylmethylamine ligands (R-DPAH) have been investigated as catalysts for the cis-dihydroxylation of olefins to model the action of Rieske dioxygenases that catalyze arene cis-dihydroxylation. The Rieske dioxygenases have a mononuclear iron active site coordinated to a 2-histidine-1-carboxylate facial triad motif. The R-DPAH ligands are designed to provide a facial N,N,O-ligand set that mimics the enzyme active site. The iron(II) complexes of the R-DPAH ligands activate H2O2 to effect the oxidation of olefin substrates into cis-diol products. As much as 90% of the H2O2 oxidant is converted into cis-diol, but a large excess of olefin is required to achieve the high conversion efficiency. Reactivity and mechanistic comparisons with the previously characterized Fe(TPA)/H2O2 catalyst/oxidant combination (TPA = tris(pyridin-2-ylmethyl)amine) lead us to postulate an Fe-II/Fe-IV redox cycle for the Fe(R-DPAH) catalysts in which an Fe-IV(OH)(2) oxidant carries out the cis-hydroxylation of olefins. This hypothesis is supported by three sets of observations: (a) the absence of a lag phase in the conversion of the H2O2 oxidant into a cis-diol product, thereby excluding the prior oxidation of the Fe(II) catalyst to an Fe(III) derivative as established for the Fe(TPA) catalyst; (b) the incorporation of (H2O)-O-18 into the cis-diol product, thereby requiring O-O bond cleavage to occur prior to cis-diol formation; and (c) the formation of cis-diol as the major product of cyclohexene oxidation, rather than the epoxide or allylic alcohol products more commonly observed in metal-catalyzed oxidations of cyclohexene, implicating an oxidant less prone to oxo transfer or H-atom abstraction.