10.1021/ic302506e.s002 David W. Shaffer David W. Shaffer Géza Szigethy Géza Szigethy Joseph W. Ziller Joseph W. Ziller Alan F. Heyduk Alan F. Heyduk Synthesis and Characterization of a Redox-Active Bis(thiophenolato)amide Ligand, [SNS]<sup>3–</sup>, and the Homoleptic Tungsten Complexes, W[SNS]<sub>2</sub> and W[ONO]<sub>2</sub> American Chemical Society 2013 redox behavior ligand Homoleptic Tungsten Complexes bi tungsten complexes show SNS electrochemical data 2013-02-18 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Synthesis_and_Characterization_of_a_Redox_Active_Bis_thiophenolato_amide_Ligand_SNS_sup_3_sup_and_the_Homoleptic_Tungsten_Complexes_W_SNS_sub_2_sub_and_W_ONO_sub_2_sub_/2442508 A new tridentate redox-active ligand platform, derived from bis­(2-mercapto-<i>p</i>-tolyl)­amine, [SNS<sup>cat</sup>]­H<sub>3</sub>, has been prepared in high yields by a four-step procedure starting from commericially available bis­(<i>p</i>-tolyl)­amine. The redox-active pincer-type ligand has been coordinated to tungsten to afford the six-coordinate, homoleptic complex W­[SNS]<sub>2</sub>. To benchmark the redox behavior of the [SNS] ligand, the analogous tungsten complex of the well-known redox-active bis­(3,5-di-<i>tert</i>-butylphenolato)­amide ligand, W­[ONO]<sub>2</sub>, also has been prepared. Both complexes show two reversible reductions and two partially reversible oxidations. Structural, spectroscopic, and electrochemical data all indicate that W­[ONO]<sub>2</sub> is best described as a tungsten­(VI) metal center coordinated to two [ONO<sup>cat</sup>]<sup>3–</sup> ligands. In contrast, experimental data suggests a higher degree of S→W π donation, giving the W­[SNS]<sub>2</sub> complex non-innocent electronic character that can be described as a tungsten­(IV) metal center coordinated to two [SNS<sup>sq</sup>]<sup>2–</sup> ligands.