Disulfide reductive elimination from an iron(III) complex

作者：Wong Janice L; Sanchez Raul Hernandez; Logan Jennifer Glancy; Zarkesh Ryan A; Ziller Joseph W; Heyduk Alan F^*

来源：Chemical Science, 2013, 4(4): 1906-1910.

DOI：10.1039/c3sc22335c

The redox-active pincer ligand derived from bis(3,5-di-tert-butyl-2-phenol)amine, [ONOcat]H-3, enables reductive elimination of di-tert-butyldisulfide from a putative iron(III) dithiolate complex. The quinonate synthon of the ligand, [ONOq]K, was used to prepare [ONOq]FeX2 complexes (1, X = Cl; 2, X = N(SiMe3)(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 [ONOq]Fe(ortho-C6O2Cl4)(py) (3) or dimeric {[ONOq] Fe(ortho-C6O2Cl4)}(2) (4). In contrast, the protonolysis of 2 with tert-butylthiol resulted in the extrusion of di-tert-butyldisulfide and the formation of a [ONOcat]Fe fragment trapped with pyridine as monomeric [ONOcat]Fe(py)(3) (5) or dimeric {[ONOcat]Fe(py)}(2) (6). These results indicate that the [ONO]Fe platform can promote reductive elimination of disulfide without incurring changes to the metal oxidation state.

• 出版日期2013