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

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2023 Feb 28

PMID 36854169

Authors

Xiuxiu Yang

Edward J Reijerse

Nils Nothling

Daniel J SantaLucia

Markus Leutzsch

Alexander Schnegg

Josep Cornella

Affiliations

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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 = 1/2 state. High-resolution multifrequency EPR at the X-, Q-, and W-band enable the precise assignment of the full - and Bi -tensors. Experimental data and DFT calculations reveal both complexes are metal-centered radicals with little delocalization onto the ligands.

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