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

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 209 Bi A -tensors. Experimental data and DFT calculations reveal both complexes are metal-centered radicals with little delocalization onto the ligands.