Sidney E Creutz1, Jonas C Peters1. 1. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
Abstract
All known nitrogenase cofactors are rich in both sulfur and iron and are presumed capable of binding and reducing N2. Nonetheless, synthetic examples of transition metal model complexes that bind N2 and also feature sulfur donor ligands remain scarce. We report herein an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. A new binucleating ligand scaffold is introduced that supports an Fe(μ-SAr)Fe diiron subunit that coordinates dinitrogen (N2-Fe(μ-SAr)Fe-N2) across at least three oxidation states (Fe(II)Fe(II), Fe(II)Fe(I), and Fe(I)Fe(I)). The (N2-Fe(μ-SAr)Fe-N2) system undergoes reduction of the bound N2 to produce NH3 (∼50% yield) and can efficiently catalyze the disproportionation of N2H4 to NH3 and N2. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Synthetic model complexes of these types are desirable to ultimately constrain hypotheses regarding Fe-mediated nitrogen fixation in synthetic and biological systems.
All known pan class="Chemical">nitrogenase cofactors are rich in both pan class="Chemical">sulfur and iron and are presumed capable of binding and reducing N2. Nonetheless, synthetic examples of transition metal model complexes that bind N2 and also feature sulfurdonor ligands remain scarce. We report herein an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. A new binucleating ligand scaffold is introduced that supports an Fe(μ-SAr)Fediiron subunit that coordinates dinitrogen(N2-Fe(μ-SAr)Fe-N2) across at least three oxidation states (Fe(II)Fe(II), Fe(II)Fe(I), and Fe(I)Fe(I)). The (N2-Fe(μ-SAr)Fe-N2) system undergoes reduction of the bound N2 to produce NH3 (∼50% yield) and can efficiently catalyze the disproportionation of N2H4 to NH3 and N2. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Synthetic model complexes of these types are desirable to ultimately constrain hypotheses regarding Fe-mediated nitrogen fixation in synthetic and biological systems.
Authors: Oliver Einsle; F Akif Tezcan; Susana L A Andrade; Benedikt Schmid; Mika Yoshida; James B Howard; Douglas C Rees Journal: Science Date: 2002-09-06 Impact factor: 47.728
Authors: Thomas Spatzal; Müge Aksoyoglu; Limei Zhang; Susana L A Andrade; Erik Schleicher; Stefan Weber; Douglas C Rees; Oliver Einsle Journal: Science Date: 2011-11-18 Impact factor: 47.728
Authors: Amy L Speelman; Ilija Čorić; Casey Van Stappen; Serena DeBeer; Brandon Q Mercado; Patrick L Holland Journal: J Am Chem Soc Date: 2019-08-12 Impact factor: 15.419
Authors: Amymarie K Bartholomew; Cristin E Juda; Jonathon N Nessralla; Benjamin Lin; SuYin Grass Wang; Yu-Sheng Chen; Theodore A Betley Journal: Angew Chem Int Ed Engl Date: 2019-03-27 Impact factor: 15.336
Authors: Laura M Thierer; Sam H Brooks; Alexander B Weberg; Peng Cui; Shaoguang Zhang; Michael R Gau; Brian C Manor; Patrick J Carroll; Neil C Tomson Journal: Inorg Chem Date: 2022-04-14 Impact factor: 5.436