Dithiolate‐Bridged Fe‐Ni‐Fe Trinuclear Complexes Consisting of Fe(CO)3−n(CN)n (n=0, 1) Components Relevant to the Active Site of [NiFe] Hydrogenase

Abstract

A dithiolate-bridged Fe-Ni-Fe trinuclear carbonyl complex [(CO)(3)Fe(mu-ndt)Ni(mu-ndt)Fe(CO)(3)] (1, ndt = norbornane-exo-2,3-dithiolate) has been synthesized from the reaction of [Fe(CO)(4)I(2)] and Li(2)[Ni(ndt)(2)]. This reaction was found to occur with concomitant formation of a tetranuclear cluster [Ni(3)(mu-ndt)(4)FeI] (2). Treatment of 1 with Na[N(SiMe(3))(2)] transforms some of the CO ligands into CN(-), and the monocyanide complex (PPh(4))[(CO)(2)(CN)Fe(mu-ndt)Ni(mu-ndt)Fe(CO)(3)] (3) and the dicyanide complex (PPh(4))(2)[(CO)(2)(CN)Fe(mu-ndt)Ni(mu-ndt)Fe(CO)(2)(CN)] (4) were isolated. X-ray structural analyses of the trinuclear complexes revealed a Fe-Ni-Fe array in which the metal centers are connected by the ndt sulfur bridges and direct Fe-Ni bonds. Hydrogen bonding between the CN ligand in 3 and cocrystallized ethanol was found in the solid-state structure. The monocyanide complex 3 and dicyanide complex 4 reacted with acids such as HOTf or HCl generating insoluble materials, whereas complex 1 did not react.