Here, we describe the synthesis and characterization of the two mu-hydrido models of [NiFe]H(2)ases prepared from a new type of H-2 activation by the corresponding two mu-hydroxo models. In addition, another mu-hydrido model prepared by the anionic exchange between one of the two mu-hydrido models and KPF6 is also reported. Interestingly, the synthesis of the two mu-hydrido models from H-2 activation represents the first functional modeling of the H-2 activation catalyzed by the [NiFe]H(2)ase (Ni-SIr)(1) state to give the Ni-R state.