Targeting synthetic analogues of the metallo-sulfur active sites of nickel enzymes capable of important catalysis

The nickel containing enzymes NiFe-hydrogenase, carbon monoxide dehydrogenase and acetyl-CoA synthase are able to catalyse environmentally, and potentially industrially, important reactions: hydrogen uptake; carbon dioxide/carbon monoxide interconversion; and incorporation of carbon monoxide to form acetyl-CoA, respectively. Progress toward the synthesis of nickel-iron complexes with structural features related to the active sites of these enzymes are described, together with the synthesis, properties and crystal structure of the first methylated-nickel-iron diheterometallic complex, [{Fe(NS3)(NO)-S}Ni(CH3)(dppe)](NS3= N(CH2CH2S)33-), relevant to a proposed mechanistic intermediate in the acetyl-CoA synthase mechanism.