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PreprintCC BYChemRxiv

Redox-active ligand facilitates HNO generation in a super-reduced dinitrosyl iron complex

  • Esther Mosebolatan1,2
  • Aruzhan Abdikaiym1,3
  • Chandradeep Ghosh1,4
  • Anagha Kuruvayil1,2
  • Saikat Mishra1,2
  • Krish Pudu1,2
  • Jeffery A. Bertke1,5
  • Marek Freindorf1,2
  • Brad S. Pierce1,3
  • Paul A. Lindahl1,4,6
  • Pokhraj Ghosh1,2
6 affiliations
  1. 1Department of Chemistry
  2. 2Southern Methodist University
  3. 3University of Alabama
  4. 4Texas A&M University
  5. 5Georgetown University
  6. 6Department of Biochemistry and Biophysics
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Abstract

Dinitrosyl iron complexes (DNICs) are widespread biological nitric oxide (NO) storage and delivery motifs, yet their highly delocalized electronic structure generally resists NO-centered reductive chemistry. Here, we establish ligandcentered reduction as a strategy for unlocking nitroxyl (HNO)-generating DNIC reactivity. A redox-active formazanate ligand (L) stabilizes a super-reduced formal {LFe(NO) 2 } 11 state beyond the conventional {Fe(NO) 2 } 9/10 redox pair. EPR and Mössbauer spectroscopy, together with density functional theory calculations, identify predominantly ligand-centered reduction, yielding an {Fe(NO) 2 } 10 unit coupled to a formazanate radical dianion, L 2−• . Electronic communication between the reduced ligand and the [Fe(NO) 2 ] unit enhances Fe-to-NO π backbonding, consistent with experimental ν(NO) redshifts. Importantly, protonation triggers HNO release, representing an unprecedented example of HNO generation from the super reduced DNIC scaffold. Isotopically distinct H 14 NO/H 15 NO is trapped with PPh 3 , along with the 14/15 N 2 O characterization. Calculations support direct nitrosyl protonation to form an Fe-bound HNO intermediate, followed by solvent-assisted HNO release and subsequent N 2 O formation. These findings establish that ligand-centered electron accommodation coupled to nitrosyl protonation enables HNO generation from a formally super-reduced DNIC, extending DNIC reactivity beyond conventional NO donation.

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Cite

BibTeXRIS
BibTeX
@misc{mosebolatan2026redoxactive,
  title = {{Redox-active ligand facilitates HNO generation in a super-reduced dinitrosyl iron complex}},
  author = {Esther Mosebolatan and Aruzhan Abdikaiym and Chandradeep Ghosh and Anagha Kuruvayil and Saikat Mishra and Krish Pudu and Jeffery A. Bertke and Marek Freindorf and Brad S. Pierce and Paul A. Lindahl and Pokhraj Ghosh},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15011062/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011062/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Redox-active ligand facilitates HNO generation in a super-reduced dinitrosyl iron complex
AU  - Esther Mosebolatan
AU  - Aruzhan Abdikaiym
AU  - Chandradeep Ghosh
AU  - Anagha Kuruvayil
AU  - Saikat Mishra
AU  - Krish Pudu
AU  - Jeffery A. Bertke
AU  - Marek Freindorf
AU  - Brad S. Pierce
AU  - Paul A. Lindahl
AU  - Pokhraj Ghosh
PY  - 2026
DA  - 2026/10/26
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15011062/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011062/v1
AB  - Dinitrosyl iron complexes (DNICs) are widespread biological nitric oxide (NO) storage and delivery motifs, yet their highly delocalized electronic structure generally resists NO-centered reductive chemistry. Here, we establish ligandcentered reduction as a strategy for unlocking nitroxyl (HNO)-generating DNIC reactivity. A redox-active formazanate ligand (L) stabilizes a super-reduced formal {LFe(NO) 2 } 11 state beyond the conventional {Fe(NO) 2 } 9/10 redox pair. EPR and Mössbauer spectroscopy, together with density functional theory calculations, identify predominantly ligand-centered reduction, yielding an {Fe(NO) 2 } 10 unit coupled to a formazanate radical dianion, L 2−• . Electronic communication between the reduced ligand and the [Fe(NO) 2 ] unit enhances Fe-to-NO π backbonding, consistent with experimental ν(NO) redshifts. Importantly, protonation triggers HNO release, representing an unprecedented example of HNO generation from the super reduced DNIC scaffold. Isotopically distinct H 14 NO/H 15 NO is trapped with PPh 3 , along with the 14/15 N 2 O characterization. Calculations support direct nitrosyl protonation to form an Fe-bound HNO intermediate, followed by solvent-assisted HNO release and subsequent N 2 O formation. These findings establish that ligand-centered electron accommodation coupled to nitrosyl protonation enables HNO generation from a formally super-reduced DNIC, extending DNIC reactivity beyond conventional NO donation.
ER  -