A mononuclear iron­(II) complex FeII(N4PyMe2)­(OTf)­(OTf)­(1), supported by a new pentadentate ligand, bis­(6-methylpyridin-2-yl)-N,N-bis­((pyridin-2-yl)­methyl)­methanamine (N4PyMe2), has been isolated and characterized. Introduction of methyl groups in the 6-position of two pyridine rings makes the N4PyMe2 a weaker field ligand compared to the parent N4Py ligand. Complex 1 is high-spin in the solid state and converts to FeII(N4PyMe2)­(CH3CN)­(OTf)2 (1a) in acetonitrile solution. The iron­(II) complex in acetonitrile displays temperature-dependent spin-crossover behavior over a wide range of temperature. In its reaction with m-CPBA or oxone in acetonitrile at −10 °C, the iron­(II) complex converts to an iron­(IV)-oxo species, FeIV(O)­(N4PyMe2)2+ (2). Complex 2 exhibits the Mössbauer parameters δ = 0.05 mm/s and ΔE Q = 0.62 mm/s, typical of N-ligated S = 1 iron­(IV)-oxo species. The iron­(IV)-oxo complex has a half-life of only 14 min at 25 °C and is reactive toward oxygen-atom-transfer and hydrogen-atom-transfer (HAT) reactions. Compared to the parent complex FeIV(O)­(N4Py)2+, 2 is more reactive in oxidizing thioanisole and oxygenates the C–H bonds of aliphatic substrates including that of cyclohexane. The enhanced reactivity of 2 toward cyclohexane results from the involvement of the S = 2 transition state in the HAT pathway and a lower triplet-quintet splitting compared to FeIV(O)­(N4Py)2+, as supported by DFT calculations. The second-order rate constants for HAT by 2 is well correlated with the C–H bond dissociation energies of aliphatic substrates. Surprisingly, the slope of this correlation is different from that of FeIV(O)­(N4Py)2+, and 2 is more reactive only in the case of strong C–H bonds (>86 kcal/mol), but less reactive in the case of weaker C–H bonds. Using oxone as the oxidant, the iron­(II) complex displays catalytic oxidations of substrates with low activity but with good selectivity.