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.