Sequential one-electron redox processes in a homoleptic rhodium complex supported by a bis(sulfidophosphoranyl)triazine pincer framework
Electrochimica Acta, vol. 574, pp. 149218
Abstract
ABSTRACT The stabilization of open-shell configurations in rhodium chemistry remains challenging because rhodium typically favors two-electron reactivity between the +I and +III oxidation states. Herein, we report a homoleptic Rh(III) complex supported by two bis(sulfidophosphoranyl)triazine pincer ligands that enables access to multiple sequential one-electron reduction events. Spectroelectrochemistry and EPR demonstrate that the first reduction generates an S = 1/2 species featuring substantial metal–ligand spin delocalization, consistent with a non-innocent ligand framework. Subsequent reductions are accompanied by coordination reorganization and ligand dissociation, underscoring the dynamic redox behavior of the system and emphasizing the blurred boundary between metal- and ligand-centered redox processes. Overall, these results illustrate how a bis(sulfidophosphoranyl)triazine platform can promote multi-step one-electron redox chemistry in a mononuclear rhodium complex while revealing how redox-active ligands affect conventional oxidation-state descriptions.
Authors 8
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Max Planck Institute for Chemical Energy Conversion · RWTH Aachen University
Affiliation as printed
Institut für Technische und Makromolekulare Chemie (ITMC), RWTH Aachen University, Worringer Weg 2, 52074 Aachen, Germany
Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34 - 36, 45470 Mülheim an der Ruhr, Germany
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Max Planck Institute for Chemical Energy Conversion
Affiliation as printed
Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34 - 36, 45470 Mülheim an der Ruhr, Germany
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Max-Planck-Institut für Kohlenforschung
Affiliation as printed
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
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Max Planck Institute for Chemical Energy Conversion
Affiliation as printed
Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34 - 36, 45470 Mülheim an der Ruhr, Germany
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Max Planck Institute for Chemical Energy Conversion
Affiliation as printed
Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34 - 36, 45470 Mülheim an der Ruhr, Germany
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Max Planck Institute for Chemical Energy Conversion · RWTH Aachen University
Affiliation as printed
Institut für Technische und Makromolekulare Chemie (ITMC), RWTH Aachen University, Worringer Weg 2, 52074 Aachen, Germany
Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34 - 36, 45470 Mülheim an der Ruhr, Germany
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Nicolas Kaeffer corresponding
Centre National de la Recherche Scientifique · Université de Haute-Alsace · Max Planck Institute for Chemical Energy Conversion · Laboratoire d'innovation moléculaire et applications · Université de Strasbourg
Affiliation as printed
Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34 - 36, 45470 Mülheim an der Ruhr, Germany
Université de Strasbourg, Université de Haute-Alsace, CNRS, LIMA, UMR 7042, 67000 Strasbourg, France
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Christophe Werlé corresponding
Centre National de la Recherche Scientifique · Max Planck Institute for Chemical Energy Conversion · Laboratoire Lorrain de Chimie Moléculaire · Université de Lorraine
Affiliation as printed
Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34 - 36, 45470 Mülheim an der Ruhr, Germany
Université de Lorraine, CNRS, L2CM, F-54000 Nancy, France
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