Inorganic Chemistry p. 1965 - 1974 (2021)
Update date:2022-08-02
Topics:
Speelman, Amy L.
Skubi, Kazimer L.
Mercado, Brandon Q.
Holland, Patrick L.
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.
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(2016)