Dithioate bridging Ni-Fe complexes [(dppe)Ni-II(mu-SEt)(2)-Fe-II(CN)(2)(CO)(2)](6) and [(dppe)Ni-II(mu-pdt)Fe-II(CN)(2)(CO)(2)] (dppe = 1,2-bis(diphenylphosphino)ethane and pdt=1,3-propanedithiolate) have been synthesized and structurally characterized as structural analogues of the active site of Ni-Fe hydrogenase enzymes. The synthesis starts from key intermediate fac-[Fe(CN)(2)(CO)(3)vertical bar](-)center dot[(dppe)Ni-II(mu-SEt)(2)Fe-II(CN)(2)(CO)(2)](6), which features a near-planar diethanethiolate-bridged Ni-Fe rhomb, and the arrangement of 2CN(-) ligands is cis to each other. In contrast, [(dppe)Ni-II(mu-pdt)Fe-II(CN)(2)(CO)(2)] shows a much more folded NiS2Fe rhomb, a short Ni-Fe distance, trans 2CN(-) ligands, and a semibridging CN- between Ni and Fe.