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  • Disulfide reductive elimina...
    Wong, Janice L; Sanchez, Raul Hernandez; Logan, Jennifer Glancy; Zarkesh, Ryan A; Ziller, Joseph W; Heyduk, Alan F

    Chemical science (Cambridge), 03/2013, Letnik: 4, Številka: 4
    Journal Article

    The redox-active pincer ligand derived from bis(3,5-di-tert-butyl-2-phenol)amine, ONO super(cat)H sub(3), enables reductive elimination of di-tert-butyldisulfide from a putative iron(iii) dithiolate complex. The quinonate synthon of the ligand, ONO super(q)K, was used to prepare ONO super(q)FeX sub(2) complexes (1, X = Cl; 2, X = N(SiMe sub(3)) sub(2)), which were characterized by single-crystal X-ray diffraction, EPR and Mossbauer spectroscopies and identified to be high-spin iron(iii) complexes. The protonolysis of 2 with tetrachlorocatechol afforded either monomeric ONO super(q)Fe(ortho-C sub(6)O sub(2)Cl sub(4) )(py) (3) or dimeric {ONO super(q)Fe(ortho-C sub(6)O sub(2)Cl sub(4))} sub(2) (4). In contrast, the protonolysis of 2 with tert-butylthiol resulted in the extrusion of di-tert-butyldisulfide and the formation of a ONO super(cat)Fe fragment trapped with pyridine as monomeric ONO super(cat)Fe(py) sub(3) (5) or dimeric {ONO super(cat)Fe(py)} sub(2) (6). These results indicate that the ONOFe platform can promote reductive elimination of disulfide without incurring changes to the metal oxidation state.