Synthesis and Reactivity of Iron Complexes with a Biomimetic SCS Pincer Ligand

Recent experimental evidence suggests that the FeMoco of nitrogenase undergoes structural rearrangement during N₂ reduction, which may result in the generation of coordinatively unsaturated iron sites with two sulfur donors and a carbon donor. In an effort to synthesize and study small-molecule model complexes with a one-carbon/two-sulfur coordination environment, we have designed two new SCS pincer ligands containing a central NHC donor accompanied by thioether- or thiolate-functionalized aryl groups. Metalation of the thioether ligand with Fe(OTf)₂ gives 6-coordinate complexes in which the SCS ligand binds meridionally. In contrast, metalation of the thiolate ligand with Fe(HMDS)₂ gives a four-coordinate pseudotetrahedral amide complex in which the ligand binds facially, illustrating the potential structural flexibility of these ligands. Reaction of the amide complex with a bulky monothiol gives a four-coordinate complex with a one-carbon/three-sulfur coordination environment that resembles the resting state of nitrogenase. Reaction of the amide complex with phenylhydrazine gives a product with a rare κ¹-bound phenylhydrazido group which undergoes N-N cleavage to give a phenylamido complex.