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Issue 4, 2013
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Disulfide reductive elimination from an iron(iii) complex

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The redox-active pincer ligand derived from bis(3,5-di-tert-butyl-2-phenol)amine, [ONOcat]H3, 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 Mössbauer 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.

Graphical abstract: Disulfide reductive elimination from an iron(iii) complex

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Article information

27 Dec 2012
08 Feb 2013
First published
22 Feb 2013

Chem. Sci., 2013,4, 1906-1910
Article type
Edge Article

Disulfide reductive elimination from an iron(III) complex

J. L. Wong, R. H. Sánchez, J. G. Logan, R. A. Zarkesh, J. W. Ziller and A. F. Heyduk, Chem. Sci., 2013, 4, 1906
DOI: 10.1039/C3SC22335C

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