α,α'-Diamino- p-tetrafluoroquinodimethane: Stability of One- and Two-Electron Oxidized Species and Fixation of Molecular Oxygen

Alok Mahata; Nicolas Chrysochos; Ivo Krummenacher; Shubhadeep Chandra; Holger Braunschweig; Carola Schulzke; Biprajit Sarkar; Cem B Yildiz; Anukul Jana

doi:10.1021/acs.joc.1c01120

α,α'-Diamino- p-tetrafluoroquinodimethane: Stability of One- and Two-Electron Oxidized Species and Fixation of Molecular Oxygen

J Org Chem. 2021 Aug 6;86(15):10467-10473. doi: 10.1021/acs.joc.1c01120. Epub 2021 Jul 16.

Authors

Alok Mahata¹, Nicolas Chrysochos², Ivo Krummenacher³, Shubhadeep Chandra⁴, Holger Braunschweig³, Carola Schulzke², Biprajit Sarkar⁴, Cem B Yildiz⁵, Anukul Jana¹

Affiliations

¹ Tata Institute of Fundamental Research Hyderabad, Gopanpally, Hyderabad 500046, Telangana, India.
² Institut für Biochemie, Universität Greifswald, Felix-Hausdorff-Straße 4, D-17489 Greifswald, Germany.
³ Institute of Inorganic Chemistry and Institute for Sustainable Chemistry and Catalysis with Boron (ICB), Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
⁴ Universität Stuttgart, Fakultät Chemie, Lehrstuhl für Anorganische Koordinationschemie, Institut für Anorganische Chemie, Pfaffenwaldring 55, D-70569 Stuttgart, Germany.
⁵ Department of Medicinal and Aromatic Plants, University of Aksaray, 68100 Aksaray, Turkey.

PMID: 34269573
DOI: 10.1021/acs.joc.1c01120

Abstract

Herein, we report the synthesis, characterization, and reactivity of α,α'-diamino-p-tetrafluoroquinodimethane, a p-tetrafluorophenylene-bridged monosubstituted carbene-based Thiele's hydrocarbon A. The compound exhibits a reversible two-step one-electron oxidation with a marginally stable radical cation state B. The in situ formation of the radical cation could be confirmed by electron paramagnetic resonance spectroscopy. Interestingly, α,α'-diamino-p-tetrafluoroquinodimethane fixates atmospheric oxygen to form a 16-membered peroxide-bridged macrocyclic compound C.