Unlocking Ligand-Centered Redox Activity in an Indenyl Framework through Phosphorus Substitution
Abstract
Herein, we show that a phosphonium-substituted diphosphaindenylide (PPIPh) functions as a genuine two-electron redox-active π-ligand. The cationic manganese complex [Mn(CO)3(η5‑PPIPh)][BArF24] ([1][BArF24]) undergoes a reversible two-electron reduction to afford the isolable anionic complex [K(18c6)][Mn(CO)3(η3‑PPIPh)]·([K(18c6)][BArF24])n (n = 1 – 5). This constitutes the first isolable and structurally characterized two-electron redox couple of an indenyl-derived manganese complex, which has previously eluded isolation with purely carbocyclic indenyl ligands. Computational studies establish manganese in the +I oxidation state in both complexes, demonstrating that the redox process is exclusively ligand-centered. The redox-activity of the ligand also translates into chemical reactivity, with the anionic complex affording 91% yield in the hydroboration of 2-acetonaphthone, compared to only 7% for [1][BArF24].
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BibTeX
@misc{zuber2026unlocking,
title = {{Unlocking Ligand-Centered Redox Activity in an Indenyl Framework through Phosphorus Substitution}},
author = {David Zuber and Michael Neuwirt and Peter Coburger},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008539/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008539/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Unlocking Ligand-Centered Redox Activity in an Indenyl Framework through Phosphorus Substitution
AU - David Zuber
AU - Michael Neuwirt
AU - Peter Coburger
PY - 2026
DA - 2026/09/09
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008539/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008539/v1
AB - Herein, we show that a phosphonium-substituted diphosphaindenylide (PPIPh) functions as a genuine two-electron redox-active π-ligand. The cationic manganese complex [Mn(CO)3(η5‑PPIPh)][BArF24] ([1][BArF24]) undergoes a reversible two-electron reduction to afford the isolable anionic complex [K(18c6)][Mn(CO)3(η3‑PPIPh)]·([K(18c6)][BArF24])n (n = 1 – 5). This constitutes the first isolable and structurally characterized two-electron redox couple of an indenyl-derived manganese complex, which has previously eluded isolation with purely carbocyclic indenyl ligands. Computational studies establish manganese in the +I oxidation state in both complexes, demonstrating that the redox process is exclusively ligand-centered. The redox-activity of the ligand also translates into chemical reactivity, with the anionic complex affording 91% yield in the hydroboration of 2-acetonaphthone, compared to only 7% for [1][BArF24].
ER -