The synthesis and characterisation of the trinuclear Ni-Fe complex [Ni(L(2))SFe(2)(CO)(6)] (1) formed from the reaction of [Ni(L(1))] with Fe(3)(CO)(12) is described. The single-crystal X-ray structure of 1 shows Ni(ii) bound to three thioether R(2)-S donors and bridged by a sulfide (S(2-)) group to two Fe(CO)(3) units. undergoes a reversible one-electron reduction process at E(1/2) = -1.62 V vs. Fc(+)/Fc to generate 1 (-), which has been characterised by UV-vis and IR spectroelectrochemistry and by EPR spectroscopy. DFT calculations on 1and 1 (-) reveal electronic structures that are delocalised across the NiFe(2) core. The SOMO in 1 (-) possesses Ni-Fe and Fe-Fe anti-bonding character and lies approximately in the plane defined by the equilateral triangle of Ni and Fe atoms. It possesses d-orbital contributions of 18.5, 15.0 and 19.8% for the Ni(1), Fe(1) and Fe(2) atoms, respectively. The Ni-S(sulfide) bond length in 1 [2.1654(7) A] is identical to that for the bridging sulfide found in the oxidised inactive form of the [NiFe] hydrogenase from D. vulgaris (2.16 A). Thus, 1 provides a useful comparison for biological [NiFe] centres bridged by sulfide donors.