Previously we have characterized two high-valent complexes [LFe(IV)(μ-O)(2)Fe(III)L], 1, and [LFe(IV)(O)(μ-O)(OH) Fe(IV)L], 4. Addition of hydroxide or fluoride to 1 produces two new complexes, 1-OH and 1-F. Electron paramagnetic resonance (EPR) and Mössbauer studies show that both complexes have an S = 1/2 ground state which results from antiferromagnetic coupling of the spins of a high-spin (S(a) = 5/2) Fe(III) and a high-spin (S(b) = 2) Fe(IV) site. 1-OH can also be obtained by a 1-electron reduction of 4, which has been shown to have an Fe(IV)═O site. Radiolytic reduction of 4 at 77 K yields a Mössbauer spectrum identical to that observed for 1-OH, showing that the latter contains an Fe(IV)═O. Interestingly, the Fe(IV)═O moiety has S(b) = 1 in 4 and S(b) = 2 in 1-OH and 1-F. From the temperature dependence of the S = 1/2 signal we have determined the exchange coupling constant J (ℋ = JS(a)·S(b) convention) to be 90 ± 20 cm(-1) for both 1-OH and 1-F. Broken-symmetry density functional theory (DFT) calculations yield J = 135 cm(-1) for 1-OH and J = 104 cm(-1) for 1-F, in good agreement with the experiments. DFT analysis shows that the S(b) = 1 → S(b) = 2 transition of the Fe(IV)═O site upon reduction of the Fe(IV)-OH site to high-spin Fe(III) is driven primarily by the strong antiferromagnetic exchange in the (S(a) = 5/2, S(b) = 2) couple.