The design of iron clusters featuring a bimetallic core and several protonation sites in the second coordination sphere of the metal centers is important for modeling the activity of polymetallic active sites such as the H-cluster of [FeFe]-hydrogenases. For this purpose, the syntheses of complexes [Fe3(CO)5(κ2-PPh2NR2)(μ-pdt)2] (R = Ph (1), Bn (2)) and [Fe3(CO)5(κ2-PPh2NR2)(μ-adtBn)(μ-pdt)] (R = Ph (3), Bn (4)) were carried out by reacting hexacarbonyl precursors [Fe2(CO)6(µ-xdt)] (xdt = pdt (propanedithiolate), adtBn (azadithiolate) with mononuclear complexes [Fe(κ2-pdt)(CO)2(κ2-PPh2NR2)] (PPh2NR2 = (PPhCH2NRCH2)2, R = Ph, Bn) in order to introduce amine functions, through well-known PPh2NR2 diphosphine, into the vicinity of the triiron core. The investigation of the reactivity of these triiron species towards the proton (in the presence of CF3SO3H) and the influence of the pendant amines on the redox properties of these complexes were explored using spectroscopic and electrochemical methods. The protonation sites in such triiron clusters and their relationships were identified. The orientation of the first and second protonation processes depends on the arrangement of the second coordination sphere. The similarities and differences, due to the extended metal nuclearity, with their dinuclear counterparts [Fe2(CO)4(κ2-PPh2NR2)(μ-pdt)], were highlighted.