Diiron models for active site of FeFe-hydrogenase with aromatic thiolate bridges: Structures and electrochemistry

Complexes of type Fe2(CO)6(μ-SC6H4–R)2, [R = p-H (1); o-CH3O (2); p-CH3O (3); p-Cl (4)] were synthesized by reaction of triiron dodecacarbonyl with the corresponding aromatic thiols. In the presence of an excess of PMe3, 2 was transformed to compound Fe2(CO)4(μ-SC6H4–o-CH3O)2(PMe3)2 (5). The structures and biochemical properties of these complexes, especially electrochemistry, have been studied.