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Journal Article

Synthesis, Isolation, and Characterization of Two Cationic Organobismuth(II) Pincer Complexes Relevant in Radical Redox Chemistry

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Yang,  Xiuxiu
Research Group Cornellà, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Nöthling,  Nils
Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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SantaLucia,  Daniel J.
Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Leutzsch,  Markus
Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Cornella,  Josep
Research Group Cornellà, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Yang, X., Reijerse, E. J., Nöthling, N., SantaLucia, D. J., Leutzsch, M., Schnegg, A., et al. (2023). Synthesis, Isolation, and Characterization of Two Cationic Organobismuth(II) Pincer Complexes Relevant in Radical Redox Chemistry. Journal of the American Chemical Society, 145(10), 5618-5623. doi:10.1021/jacs.2c12564.


Cite as: https://hdl.handle.net/21.11116/0000-000C-E8F8-7
Abstract
Herein, we report the synthesis, isolation, and characterization of two cationic organobismuth(II) compounds bearing N,C,N pincer frameworks, which model crucial intermediates in bismuth radical processes. X-ray crystallography uncovered a monomeric Bi(II) structure, while SQUID magnetometry in combination with NMR and EPR spectroscopy provides evidence for a paramagnetic S = 1/2 state. High-resolution multifrequency EPR at the X-, Q-, and W-band enable the precise assignment of the full g- and 209Bi A-tensors. Experimental data and DFT calculations reveal both complexes are metal-centered radicals with little delocalization onto the ligands.