Density functional theory has been used to study diiron dithiolates [HFe2(xdt)(PR3)n(CO)5-nX] (n = 0, 2, 4; R = H, Me, Et; X = CH3S(-), PMe3, NHC = 1,3-dimethylimidazol-2-ylidene; xdt = adt, pdt; adt = azadithiolate; pdt = propanedithiolate). These species are related to the [FeFe]-hydrogenases catalyzing the 2H(+) + 2e(-) ↔ H2 reaction. Our study is focused on the reduction step following protonation of the Fe2(SR)2 core. Fe(H)s detected in solution are terminal (t-H) and bridging (μ-H) hydrides. Although unstable versus μ-Hs, synthetic t-Hs feature milder reduction potentials than μ-Hs. Accordingly, attempts were previously made to hinder the isomerization of t-H to μ-H. Herein, we present another strategy: in place of preventing isomerization, μ-H could be made a stronger oxidant than t-H (E°μ-H > E°t-H). The nature and number of PR3 unusually affect ΔE°t-H-μ-H: 4PEt3 models feature a μ-H with a milder E° than t-H, whereas the 4PMe3 analogues behave oppositely. The correlation ΔE°t-H-μ-H ↔ stereoelectronic features arises from the steric strain induced by bulky Et groups in 4PEt3 derivatives. One-electron reduction alleviates intramolecular repulsions only in μ-H species, which is reflected in the loss of bridging coordination. Conversely, in t-H, the strain is retained because a bridging CO holds together the Fe2 core. That implies that E°μ-H > E°t-H in 4-PEt3 species but not in 4PMe3 analogues. Also determinant to observe E°μ-H > E°t-H is the presence of a Fe apical σ-donor because its replacement with a CO yields E°μ-H < E°t-H even in 4PEt3 species. Variants with neutral NHC and PMe3 in place of CH3S(-) still feature E°μ-H > E°t-H. Replacing pdt with (Hadt)(+) lowers E° but yields E°μ-H < E°t-H, indicating that μ-H activation can occur to the detriment of the overpotential increase. In conclusion, our results indicate that the electron richness of the Fe2 core influences ΔE°t-H-μ-H, provided that (i) the R size of PR3 must be greater than that of Me and (ii) an electron donor must be bound to Fe apically.