The development of synthetic analogs of the active sites of [NiFe] hydrogenases remains challenging, and, in spite of the number of complexes featuring a [NiFe] center, those featuring CO and CN- ligands at the Fe center are under -represented. We report herein the synthesis of three bimetallic [NiFe] complexes [Ni(N2S2)Fe(CO)(2)(CN)(2)], [Ni(S-4)Fe(CO)(2)(CN)(2)], and [Ni(N2S3)Fe(CO)(2)(CN)(2)] that each contain a Ni center that bridges through two thiolato S donors to a {Fe(CO)(2)(CN)(2)} unit. X-ray crystallographic studies on [Ni(N2S3)Fe(CO)(2)(CN)(2)], supported by DFT calculations, are consistent with a solid-state structure containing distinct molecules in the singlet (S = 0) and triplet (S = 1) states. Each cluster exhibits irreversible reduction processes between -1.45 and -1.67 V vs Fc(+)/Fc and [Ni(N2S3)Fe(CO)(2)(CN)(2)] possesses a reversible oxidation process at 0.17 V vs Fc(+)/Fc. Spectroelectrochemical infrared (IR) and electron paramagnetic resonance (EPR) studies, supported by density functional theory (DFT) calculations, are consistent with a NilliFen formulation for [Ni(N2S3)Fe(CO)(2)(CN)(2)](+). The singly occupied molecular orbital (SOMO) in [Ni(N2S3)Fe(CO)(2)(CN)(2)](+) is based on Nd-z2 and 3p S with the S contributions deriving principally from the apical S -donor. The nature of the SOMO corresponds to that proposed for the Ni C state of the [NiFe] hydrogenases for which a NilliFell formulation has also been proposed. A comparison of the experimental structures, and the electrochemical and spectroscopic properties of [Ni(N2S3)Fe(CO)(2)(CN)(2)] and its [Ni(N2S3)] precursor, together with calculations on the oxidized [Ni(N2S3)Fe(CO)(2)(CN)(2)](+) and [Ni(N2S3)](+) forms suggests that the binding of the {Fe(CO)(CN)(2)} unit to the {Ni(CysS)(4)} center at the active site of the [NiFe] hydrogenases suppresses thiolate-based oxidative chemistry involving the bridging thiolate S donors. This is in addition to the role of the Fe center in modulating the redox potential and geometry and supporting a bridging hydride species between the Ni and Fe centers in the Ni-C state.