A Dithiolato And Hydrido Bridged (Co/Cn)Fe-Ni Complex With Unprotected Cn: A Model For The [Ni-R] State Of The [Ni-Fe] Hydrogenase Active Site

A dithiolate/hydride bridged Fe-Ni complex, [(CN)(CO)(2)Fe-II(mu-pdt)(mu-H)Ni-II(CN)(PCy3)](-)(2, pdt = propane-1,3-dithiolate) has been synthesized by the reaction of [(CN)(2)(CO)(2)Fe-II(pdt)](2-) with [Ni-II(Cl)(H)(PCy3)(2)] as a synthetic analogue of the Ni-R state of the active site of the [Ni-Fe] hydrogenase. X-ray crystallography of this model complex suggests that the hydride unsymmetrically binds to Ni and Fe similar to natural [Ni-Fe] hydrogenases.